Modified fillers and elastomeric composites comprising same

ABSTRACT

Modified fillers are described which have adsorbed and/or attached chemical groups, such as a triazole and/or pyrazole thereon. Other modified fillers are also described. Elastomeric compositions containing the modified filler are further described, as well as methods to improve hysteresis and/or abrasion resistance in elastomeric compositions using the modified fillers of the present invention.

The present application is a continuation of International PatentApplication No. PCT/US2011/050298, filed on Sep. 2, 2011, which, inturn, claims priority under 35 U.S.C. §119(e) of prior U.S. ProvisionalPatent Application No. 61/380,032, filed Sep. 3, 2010, which isincorporated in its entirety by reference herein.

BACKGROUND OF THE INVENTION

The present invention relates to fillers, elastomeric compositions orcomposites, and methods to make the same, and methods to improve one ormore properties in elastomeric compositions. More specifically, thepresent invention relates to modified fillers and the use of thesefillers in elastomeric compositions.

Carbon blacks and other fillers have been utilized as pigments, fillers,and/or reinforcing agents in the compounding and preparation ofcompositions used in rubber, plastic, paper or textile applications. Theproperties of the carbon black or other fillers are important factors indetermining various performance characteristics of these compositions.

Much effort has been expended over the last several decades to modifythe surface chemistry of carbon black. Useful processes for attaching anorganic group to carbon black and uses of the resulting product aredescribed, for example, in U.S. Pat. Nos. 5,559,169; 5,900,029;5,851,280; 6,042,643; 6,494,946; 6,740,151; and 7,294,185, all of whichare incorporated herein by reference in their entirety. U.S. Pat. No.5,559,169, for example, discloses a carbon black product having anattached organic group of the formula —Ar—S_(n)—Ar′— or —Ar—S_(n)—Ar″—(where Ar and Ar′ are arylene groups, Ar″ is an aryl group and n is 1 to8) that can be employed in ethylene-propylene-diene monomers (EPDM),partially hydrogenated copolymer of acrylonitrile and butadiene (HNBR),or butyl rubber compositions.

Important uses of elastomeric compositions relate to the manufacture oftires and additional ingredients often are added to impart specificproperties to the finished product or its components. U.S. Pat. No.6,014,998, for example, describes the use of benzotriazole ortolyltriazole to improve cure rates, cure efficiency, hardness, staticand dynamic moduli, without adversely affecting hysteresis insilica-reinforced rubber compositions for tire components. Thesecompositions include from about 2 to about 35 parts triazoles(preferably from about 2 to about 6 parts triazoles) per hundred partsof rubber. In some cases, brass powder and conductive carbon black arealso added and the compositions are mixed by conventional means in oneor multiple steps.

U.S. Pat. No. 6,758,891 relates to the treatment of carbon black,graphite powder, graphite fibers, carbon fibers, carbon fibrils, carbonnanotubes, carbon fabrics, glass-like carbon products and active carbonby the reaction with triazene modifying agents. The resulting carbon canbe used in rubber, plastics, printing inks, inks, inkjet inks, lacquers,toners and colorants, bitumen, concrete, other constructional materials,and paper.

As indicated above, fillers can provide reinforcing benefits to avariety of materials, including elastomeric compositions. Besides theconventional filler attributes, there is a desire to provide fillerswhich can improve one or more elastomeric properties, especiallyhysteresis and/or abrasion resistance. However, in the past, with someelastomeric compositions using fillers, a filler can typically improveone property, but to the detriment of the other property. For instance,while hysteresis may improve, abrasion resistance can decrease or haveno improvement. Thus, there is a need to provide fillers whichpreferably can enhance one of these properties without any significantdetriment to the other. Even more preferable would be a filler that canimprove both properties, namely improve hysteresis and improve abrasionresistance.

SUMMARY OF THE PRESENT INVENTION

A feature of the present invention is to provide new classes of fillersthat promote one or more beneficial properties.

A further feature of the present invention is to provide fillers whichcan have the ability to improve hysteresis in elastomeric compositionswhen present.

An additional feature of the present invention is to provide a fillerthat can have the ability to improve abrasion resistance in anelastomeric composition when present.

A further feature of the present invention is to provide methods toachieve a balance of properties with respect to hysteresis and abrasionresistance in elastomeric compositions.

Additional features and advantages of the present invention will be setforth in part in the description that follows, and in part will beapparent from the description, or may be learned by practice of thepresent invention. The features and other advantages of the presentinvention will be realized and attained by means of the elements andcombinations particularly pointed out in the description and appendedclaims.

To achieve these and other advantages, and in accordance with thepurposes of the present invention, as embodied and broadly describedherein, the present invention relates to a modified filler, such as amodified carbon black, modified metal oxide, a modified filler having acarbon phase and a silicon-containing species phase, and the like. Themodified filler can be a filler having adsorbed thereon at least onetriazole, or at least one pyrazole, or any combinations thereof. Morespecific formulas and examples are provided.

This modified filler can optionally have attached at least one chemicalgroup, such as an organic group, for instance, an organic groupcomprising at least one alkyl group and/or aromatic group. The alkylgroup and/or aromatic group can be directly attached to the filler. Thechemical group can be the same or similar or different to the group thatis adsorbed onto the filler. The chemical group attached can be orinclude at least one triazole, or at least one pyrazole, or at least oneimidazole, or any combinations thereof.

The present invention also relates to a modified filler, such as amodified carbon black or modified metal oxide or the like, havingattached thereon at least one triazole.

The present invention further relates to elastomeric compositionscontaining any one or more of the modified fillers of the presentinvention and at least one elastomer, and methods to make the same.

The present invention further relates to articles made from orcontaining one or more modified fillers of the present invention and/orone or more elastomeric compositions or polymeric compositions of thepresent invention, such as a tire or part thereof, and other elastomericand/or polymeric articles.

The present invention further relates to a method to improve hysteresisand/or abrasion resistance in an elastomeric composition, such as a tireor part thereof, by incorporating one or more modified fillers of thepresent invention into an elastomeric composition.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are intended to provide a further explanation of the presentinvention, as claimed.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The present invention relates to modified fillers, elastomericcompositions containing the modified fillers, articles made from orcontaining the modified fillers or elastomeric or other polymericcompositions, methods to make the same, and methods of improvingelastomeric properties including, but not limited to, hysteresis and/orabrasion resistance.

In more detail, the present invention relates, in part, to a modifiedfiller that is or includes a filler having adsorbed thereon: (a) atleast one triazole, such as 1,2,4 triazole; (b) at least one pyrazole;or any combinations thereof. The modified filler preferably improvesabrasion resistance when present in an elastomeric composition comparedto the same filler that is not modified (i.e., compared to an untreatedor unmodified filler). The elastomeric composition used to confirm thistest parameter can be one of the elastomeric compositions used in theExamples.

The present invention also relates, in part, to a modified filler thatis or includes a filler having adsorbed thereon:

a) at least one triazole, such as at least one 1,2,4 triazole, having asulfur-containing or poly-sulfur containing substituent, in the presenceof or absence of any other aromatic group; or

b) at least one pyrazole having a sulfur-containing substituent in thepresence of or absence of any other aromatic group, or any combinationsthereof. Again, preferably, the modified filler improves abrasionresistance when present in an elastomeric composition compared to thefiller that is not modified. Again, to confirm this test property, oneof the elastomeric compositions used in the Examples can be used.

For purposes of the present invention, the adsorbing of (a) and/or (b)means that the adsorbed chemical group is not chemically attached ontothe surface of the filler and can be removed from the surface by asolvent extraction, such as a Soxhlet extraction. For example, achemical group that is adsorbed onto the filler can be removed bySoxhlet extraction that can occur for 16-18 hours in methanol orethanol, wherein the extraction removes all, or nearly or substantiallyall, of the chemical group. The extraction can be repeated one or moretimes. It is possible that a residual of the adsorbed group can remainon the surface of the filler. For purposes of the present invention, theextraction by solvent, as described herein, can remove at least 80 wt %of the adsorbed chemical group and, generally, at least 90% or at least95% by weight of the adsorbed chemical group. This determination can bemade by an elemental analysis of extracted and unextracted samples.

For purposes of the present invention, the triazole includes a chemicalgroup that has a triazole-containing group. The triazole can be a 1,2,4triazole or a 1,2,3 triazole. The triazole can be a thiol orpolysulfide-containing polytriazole. 1,2,4 triazole or 1,2,4triazole-containing groups are preferred as adsorbed chemical groups.Examples of the triazole include a triazole having the formula (ortautomers thereof):

or a triazole (or tautomers thereof) having the formula:

wherein Z_(b) is an alkylene group (e.g., C₁-C₄ alkylene), wherein b is0 or 1;

X, which is the same or different, is H, NH₂, SH, NHNH₂, CHO, COOR,COOH, CONR₂, CN, CH₃, OH, NDD′, or CF₃;

Y is H, or NH₂;

A is a functional group and can be or comprise S_(k)R, SSO₃H, SO₂NRR′,SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), or 2-(1,3-dithiolanyl); or a linear, branched,aromatic, or cyclic hydrocarbon radical substituted with one or more ofthe functional groups;

where R and R′, which can be the same or different, are hydrogen;branched or unbranched C₁-C₁₂ unsubstituted or substituted alkyl,alkenyl, alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl;unsubstituted or substituted arylalkyl, arylene, heteroarylene, oralkylarylene;

k is an integer from 1 to 8; and

Q is (CH₂)_(w), (CH2)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂), where x is 1 to 6, z is 1 to 6, and w is 2 to 6. S_(k)Rcan be S_(k)H. For S_(k)R, when R is not H, k is 2 to 8, and when R isH, k is 1 to 8;

E is a polysulfur-containing group, such as S_(w) (where w is 2 to 8),SSO, SSO₂, SOSO₂, SO₂SO₂; and

the triazole can optionally be N-substituted with an NDD′ substituent,where

D and D′, which are the same or different, are H or C₁-C₄ alkyl.

More specific examples of the triazole include, but are not limited to,3-amino-1,2,4-triazole-5-thiol, 3-amino-1,2,4-triazole-5-yl-disulfide;1,2,4-triazole-3-thiol; 1,2,4-triazole-3-yl-disulfide;3-amino-1,2,4-triazole-5-yl-trisulfide;4-amino-3-hydrazino-1,2,4-triazole-5-thiol, and the like.

For purposes of the present invention, the pyrazole includes a chemicalthat has a pyrazole-containing group. The pyrazole can be a thiol orpolysulfide-containing polypyrazole. Examples of the pyrazole caninclude a pyrazole having the formula (or tautomers thereof):

or a pyrazole having the formula (or tautomers thereof):

wherein Z_(b) is an alkylene group (e.g., C₁-C₄ alkylene group), whereinb is 0 or 1;

X and Y are independently H, NH₂, SH, NHNH₂, CHO, COOR, COOH, CONR₂, CN,CH₃, OH, NDD′, or CF₃, or Y can be R, where each X and Y are the same ordifferent;

A is a functional group and can be or comprise S_(k)R, SSO₃H, SO₂NRR′,SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), or 2-(1,3-dithiolanyl); or a linear, branched,aromatic, or cyclic hydrocarbon radical substituted with one or more ofthe functional group(s);

where R and R′, which can be the same or different, are hydrogen;branched or unbranched C₁-C₁₂ unsubstituted or substituted alkyl,alkenyl, alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl;unsubstituted or substituted arylalkyl, arylene, heteroarylene, oralkylarylene; k is an integer from 1 to 8; and Q is (CH₂),(CH2)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherex is 1 to 6, z is 1 to 6, and w is 2 to 6. S_(k)R can be S_(k)H. ForS_(k)R, when R is not H, k is 2 to 8, and when R is H, k is 1 to 8. E isa polysulfur-containing group, such as S_(w) (where w is 2 to 8), SSO,SSO₂, SOSO₂, or SO₂SO₂, and

D and D′, which are the same or different, are H or C₁-C₄ alkyl.

More specific examples of the pyrazole include, but are not limited to,pyrazole-3-thiol, pyrazol-3-yl disulfide, and/or3-methyl-pyrazole-5-thiol.

For any of the formulas set forth herein, with regard to the substituentA, more specific examples include, but are not limited to, SH; SSAr,where Ar is a triazole or a pyrazole, or SSAr where Ar is a differentheterocycle.

As stated, the chemical groups adsorbed onto the filler or surface ofthe filler to create this type of the modified filler can be a singlechemical group, or two or more different types of chemical groups. Oneor more different types of triazoles can be present and/or one or moredifferent types of pyrazoles can be present, or any combinations, suchas one or more triazoles, with one or more pyrazoles, and the like. Inaddition, as an option, other chemical groups, other than the triazoleand/or pyrazole, can also additionally be present on the filler as anadsorbed chemical group.

The adsorbed chemical group can be entirely or substantially entirely onthe surface area of the exposed surface of the filler to form themodified filler or can be a lesser amount. For instance, the adsorbedchemical group can comprise at least 5% of the surface area of thefiller surface, at least 10%, at least 20%, at least 30%, at least 40%,at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, atleast 95%, at least 97%, at least 99%, or about 100%, or 100% of thesurface area on the surface of the filler.

The amount of adsorbed chemical group(s) can be any amount on thefiller. For example, the total amount of the adsorbed chemical group canbe from about 0.01 to about 10 micromoles of heterocyclic groups/m²surface area of filler, as measured by nitrogen adsorption (BET method),including from about 1 to about 8 micromoles/m², from about 2 to about 6micromoles/m², or from about 3 to about 5 micromoles/m².

The filler that receives the adsorbed chemical group(s) and/or theattached chemical group, as described herein, can be any conventionalfiller. The filler is a particulate filler. For example, the filler canbe one or more types of carbon black, one or more types of metal oxidesor metal containing fillers (e.g., an oxide or filler of or containingsilicon, magnesium, calcium, titanium, vanadium, cobalt, nickel,zirconium, tin, antimony, chromium, neodymium, lead, barium, cesium,and/or molybdenum), or one or more types of other carbon-containingfillers, such as a multi-phase aggregate comprising at least one carbonphase and at least one metal-containing species phase orsilicon-containing species phase (also known as silicon-treated carbonblack). The filler can be a silica-coated carbon black, an oxidizedcarbon black, a sulfonated carbon black, or a filler having attached oneor more chemical groups, such as organic groups. With respect to thecarbon black, the carbon black can be any ASTM-type carbon black, suchas an ASTM-100 to ASTM-1000 type carbon black. The filler can be one ormore types of reinforcing-grade fillers, tire-grade fillers, orrubber-grade fillers, such as tire-grade carbon blacks or rubber-gradecarbon blacks. Other examples of fillers include calcium carbonate,clay, talc, silicates, and the like.

The filler can be any carbon-containing filler, such as fibers,nanotubes, graphenes, and the like.

The filler or reinforcing agent, such as carbon black, can be anycommercially-available carbon black and/or silica, such as thoseprovided by Cabot Corporation, Degussa or Evonik Corporation, and thelike. There is no criticality whatsoever to the type of carbon black,silica, or other filler that can be used to form the modified filler(s)of the present invention. Thus, the fillers, such as carbon black and/orsilica can have any physical, analytical, and/or morphologicalproperties. Examples of suitable carbon blacks include those listedherein, as well as non-conductive or conductive furnace blacks, Cabot'sBlack Pearls® carbon blacks, Cabot's Vulcan® carbon blacks, Cabot'sSterling® carbon blacks, Cabot's Regal® carbon blacks, Cabot's Spheron®carbon blacks, Cabot's Monarch® carbon blacks, Cabot's Elftex® carbonblacks, Cabot's Emperor® carbon blacks, Cabot's IRX™ carbon blacks,Cabot's Mogul® carbon blacks, Cabot's CRX™ carbon blacks, Cabot's CSX™carbon blacks, Cabot's Ecoblack™ carbon blacks, Degussa's CK-3 carbonblack, Degussa's Corax® carbon blacks, Degussa's Durex® carbon blacks,Degussa's Ecorax carbon blacks, Degussa's Printex® carbon blacks,Degussa's Purex® carbon blacks. Other examples include lamp blacks,carbon black having attached chemical group(s), such as an organicgroup, silicon-treated carbon blacks, metal-treated carbon blacks,silica-coated carbon blacks, chemically-treated (e.g.,surfactant-treated) carbon black, and any grades of carbon black orsilica.

The carbon black can have one or more of the following properties. TheCTAB surface area may be 10 m²/g to 400 m²/g, such as 20 m²/g to 250m²/g or 50 m²/g to 150 m²/g. The Iodine number can be 10 m²/g to 1000m²/g, 20 m²/g to 400 m²/g, or 20 to 300 m²/g or 50 m²/g and 150 m²/g.The DBPA can be 20 mL/100 g to 300 mL/100 g, such as 30 mL/100 g to 200mL/100 g or 50 mL/100 g to 150 mL/100 g. Many suitable carbon blackstarting materials are available commercially. Representative examplesof commercial carbon blacks include, carbon blacks sold under theRegal®, Sterling® and Vulcan® trademarks available from CabotCorporation (such as Regale 330, Regale 300, Regale 90, Regale 85,Regale 80, Sterling® SO, Sterling® SO-1, Sterling® V, Sterling® VH,Sterling® NS-1, Vulcan® 10H, Vulcan® 9, Vulcan® 7H, Vulcan® 6, Vulcan®6LM, Vulcan® 3, Vulcan® M, Vulcan® 3H, Vulcan® P, Vulcan® K, Vulcan® Jand Vulcan® XC72). Carbon blacks available from other suppliers can beused. The starting carbon product can be a dual-phase particle,comprising a carbon phase and a second phase, e.g., a metal oxide orcarbide.

The filler, such as the carbon black, can have a low PAH amount. Thecarbon black can be formed so that the carbon black has a low PAH amountor commercially-available carbon black can be properly treated to removePAHs so as to form carbon blacks having a low PAH amount. The carbonblack of the present invention can have a low PAH amount with anystandard ASTM carbon black specifications, for instance with respect toiodine absorption, DBPA, crushed DBPA, CTAB, nitrogen surface area,STSA, and/or tinting strength, and the like. The carbon black can be anASTM specification carbon black, such as a N110, N121, N220, N231, N234,N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650, N660,N683, N762, N765, N774, N787, and/or N990 carbon black, which has theASTM specification properties for the particular N-series carbon black.The carbon black can have a STSA ranging from 20 m²/g to 150 m²/g orhigher. The carbon black can be any ASTM grade carbon black having thelow PAH amount, such as from a N110 ASTM carbon black to a N990 ASTMcarbon black and more preferably a N110 to N500 ASTM carbon black. Anycommercial grade of carbon black can be formed to have a low PAH amountand/or can be subsequently treated to have a low PAH amount based on thepresent invention.

For purposes of the present invention, a low PAH amount includes or isdefined by a low PAH 22. As indicated above, a PAH 22 is a measurementof PAHs as set forth in FIG. 1 of U.S. Patent Application PublicationNo. 2008/159947. For purposes of the present invention, a low PAH amountcan be defined by a low PAH 22. Examples of suitable amounts include 500ppm or less, 400 ppm or less, 300 ppm or less, 200 ppm or less, 150 ppmor less, 125 ppm or less, 100 ppm or less, 75 ppm or less, 50 ppm orless, 25 ppm or less, with respect to the amount of PAH 22 present inthe carbon black. Suitable ranges include from about 1 ppm to about 500ppm, 5 ppm to 500 ppm, 15 ppm to 500 ppm, 5 ppm to 50 ppm, 5 ppm to 100ppm, 1 ppm to 100 ppm, or 1 ppm to 30 ppm, with respect to the totalamount of PAH 22 present in the carbon black. For any of the ranges oramounts provided above, the lower limit can be 0.1 ppm, 1 ppm, 2 ppm, 5ppm, 10 ppm, or 15 ppm. The ranges can be exact or approximate (e.g.,“about 1 ppm” and the like). The ppm ranges can apply to all or anynumber of PAHs (e.g., all PAHs or one or more of the PAHs). For purposesof the present invention, the PAH22 is a measurement of the PAHsidentified in FIG. 1 of U.S. Patent Application Publication No.2008/159947 except for Benzo(j)fluoranthrene. Also, the PAH8 forpurposes of the present invention is a measurement ofBenzo(a)anthracene, Benzo(a)pyrene, Benzo(e)pyrene,Benzo(b)fluoranthrene, Benzo(j)fluoranthrene, Benzo(k)fluoranthrene,Chrysene, and Dibenzo(a,h)anthracene. BaP is a reference toBenzo(a)pyrene.

The carbon black of the present invention can have a PAH content of fromabout 0.15 to about 2 micrograms/m², such as from 0.2 to 1.5micrograms/m², or from 0.3 to 1.25 micrograms/m², or from 0.4 to 1.0micrograms/m², and the like.

In general, the carbon black can be a furnace black, channel black, lampblack, thermal black, acetylene black, plasma black, a carbon productcontaining silicon-containing species and/or metal containing species,and the like. The carbon black can be a short quench or long quenchblack.

For purposes of the present invention, a short quench carbon black canbe used and can be considered a carbon black formed by a process whereinthe carbon black, after formation from pyrolysis, is subjected a shortquench to stop the carbon black forming reactions. The short quench is aparameter of the furnace carbon black manufacturing process that assuresthe value of the CB Toluene Discoloration (tested per ASTM D1618) of95%, or lower. Examples of short quench carbon blacks include, but arenot limited to, Vulcan® 7H carbon black, Vulcan® J carbon black, Vulcan®10H carbon black, Vulcan® 10 carbon black, Vulcan® K carbon black,Vulcan® M carbon black, and N-121 carbon black. The short quench carbonblack can be a furnace carbon black. The short quench carbon black canbe a N110 to N787 ASTM carbon black. The short quench carbon black canhave any of the parameters described above with respect to PAH content,STSA, I₂No (mg/g)/STSA (m²/g) ratio, DBP, and the like.

The carbon black can be an oxidized carbon black, such as pre-oxidizedusing an oxidizing agent. Oxidizing agents include, but are not limitedto, air, oxygen gas, ozone, NO₂ (including mixtures of NO₂ and air),peroxides such as hydrogen peroxide, persulfates, including sodium,potassium, or ammonium persulfate, hypohalites such a sodiumhypochlorite, halites, halates, or perhalates (such as sodium chlorite,sodium chlorate, or sodium perchlorate), oxidizing acids such a nitricacid, and transition metal containing oxidants, such as permanganatesalts, osmium tetroxide, chromium oxides, or ceric ammonium nitrate.Mixtures of oxidants may be used, particularly mixtures of gaseousoxidants such as oxygen and ozone. In addition, carbon blacks preparedusing other surface modification methods to introduce ionic or ionizablegroups onto a pigment surface, such as chlorination and sulfonation, mayalso be used. Processes that can be employed to generate pre-oxidizedcarbon blacks are known in the art and several types of oxidized carbonblack are commercially available.

Details regarding silicon-treated carbon blacks and methods formanufacturing them are provided, for example, in U.S. Pat. Nos.5,830,930; 5,877,238; 6,028,137; and 6,323,273 B1, all incorporatedherein by reference in their entirety.

Also suitable as starting materials are silica-coated carbon blacks.Such carbon blacks are described, for example, in U.S. Pat. No.6,197,274 B1, which is incorporated herein by reference in its entirety.

Silicon-treated carbon black may be oxidized with oxidizing agents suchas, for instance, nitric acid and ozone and/or can be combined with acoupling agent, as described, e.g., in U.S. Pat. No. 6,323,273 B1.

With respect to the metal oxide, the metal oxide can be alumina,aluminum-containing filler, zinc oxide, zinc-containing filler, a silicaor silica-containing filler, such as a fumed silica or precipitatedsilica. The silica can be dispersible silica as that term is used inelastomers. More specific examples include Z1165 silica, Rhodia(Rhone-Poulenc)'s Zeosil® HDS, Evonik Industries (Degussa)'s Ultrasil®5000 GR and 7000 GR, and PPG's Hi-Sil 223, Agilon 400 and Ciptane™silicas. The metal oxide, such as silica, can have a CTAB of 100 m²/g to240 m²/g, and/or a BET of 100 to 240 m²/g; and/or a total pore volume ofat least 2.5 cm³/g and/or a DOP oil adsorption of 150 ml/100 g to 400ml/100 g.

For purposes of the present invention, the silica-containing fillerincludes any filler which contains a silica content of at least 0.1% byweight, based on the weight percent of the filler. The silica-containingfiller can contain a silica weight percent of at least 0.3 wt %, atleast 0.5 wt %, at least 1 wt %, at least 5 wt %, at least 7.5 wt %, atleast 10 wt %, at least 15 wt %, at least 17.5 wt %, at least 20 wt %,at least 25 wt %, at least 30 wt %, at least 35 wt %, at least 40 wt %,at least 50 wt %, at least 60 wt %, at least 70 wt %, at least 80 wt %,at least 90 wt %, or from 0.1 wt % to 100 wt %, from 2 wt % to 100 wt %,from 5 wt % to 99 wt %, from 10 wt % to 90 wt %, from 15 wt % to 90 wt%, from 15 wt % to 50 wt %, from 15 wt % to 35 wt %, or less than orequal to 50 wt % and any other weight percents, all weight percentsbased on the total weight of the silica-containing filler. Thesilica-containing filler can be or include precipitated silica, fumedsilica, silica-coated carbon black, and/or silicon-treated carbon black.Any of the silica-containing fillers can be chemically functionalized,such as to have attached chemical groups, such as attached organicgroups. Any combination of silica-containing fillers can be used.Further, the silica-containing filler(s) can be used in combinationwith, as an option, any non-silica-containing filler, such as carbonblack(s).

In silicon-treated carbon black, a silicon containing species, such asan oxide or carbide of silicon, is distributed through at least aportion of the carbon black aggregate as an intrinsic part of the carbonblack. Conventional carbon blacks exist in the form of aggregates, witheach aggregate consisting of a single phase, which is carbon. This phasemay exist in the form of a graphitic crystallite and/or amorphouscarbon, and is usually a mixture of the two forms. Carbon blackaggregates may be modified by depositing silicon-containing species,such as silica, on at least a portion of the surface of the carbon blackaggregates. The result may be described as silicon-coated carbon blacks.

The materials described herein as silicon-treated carbon blacks are notcarbon black aggregates which have been coated or otherwise modified,but actually represent a different kind of aggregate having two phases.One phase is carbon, which will still be present as graphiticcrystallite and/or amorphous carbon, while the second phase is silica(and possibly other silicon-containing species). Thus, thesilicon-containing species phase of the silicon-treated carbon black isan intrinsic part of the aggregate; it is distributed throughout atleast a portion of the aggregate. A variety of silicon-treated blacksare available from Cabot Corporation under the name Ecoblack™ CRX2125and CRX4210. It will be appreciated that the multiphase aggregates arequite different from the silica-coated carbon blacks mentioned above,which consist of pre-formed, single phase carbon black aggregates havingsilicon-containing species deposited on their surface. Such carbonblacks may be surface-treated in order to place a silica functionalityon the surface of the carbon black aggregate as described in, e.g., U.S.Pat. No. 6,929,783.

The silicon-treated carbon black can include silicon-containing regionsprimarily at the aggregate surface of the carbon black, but still bepart of the carbon black and/or the silicon-treated carbon black caninclude silicon-containing regions distributed throughout the carbonblack aggregate. The silicon-treated carbon black can be oxidized. Thesilicon-treated carbon black can contain from about 0.1% to about 50%silicon by weight, based on the weight of the silicon-treated carbonblack. These amounts can be from about 0.5 wt % to about 25 wt % or fromabout 2 wt % to about 15 wt % silicon, all based on the weight of thesilicon-treated carbon black.

With regard to the process to form the modified filler having anadsorbed chemical group(s), any conventional adsorption technique can beused. For instance, the chemical group that is desired to be on thefiller or on the surface of the filler to form this version of themodified filler can be dissolved in a suitable solvent and applied tothe surface of the filler, wherein the solvent can then be removed, suchas by evaporation techniques. As an alternative, the chemical to beadsorbed onto the surface of the filler to form the modified filler canbe melted. Any manner to contact the filler with the chemical to beadsorbed onto the surface of the filler can be used, such as spraycoating techniques, and the like. The chemical solution to be adsorbedon the filler can be mixed together in a pin pelletizer and the solventcan then be evaporated.

As an option, the modified filler having the adsorbed chemical group, asmentioned herein, can optionally also include the attachment of one ormore chemical groups.

For purposes of the present invention, the attachment of one or morechemical groups means that the chemical group is not adsorbed onto thesurface of the filler and cannot be removed or substantially removed bythe extraction process described earlier for purposes of removing anadsorbed chemical. The attachment of at least one chemical groupgenerally is by a chemical attachment, such as by a covalent bond.

The chemical group can be at least one organic group. The organic groupcan include or be an alkyl group and/or an aromatic group. More specificexamples include a C₁₋₂₀ alkyl group or a C₆₋₁₈ aromatic group, such asa C₁-C₁₂ alkyl group or C₆-C₁₂ aromatic group(s). Examples of attachedgroups can include an alkyl or aromatic group that has one or morefunctional groups that can be the same as substituent A describedherein. The alkyl group and/or aromatic group can be directly attachedto the filler.

A method to attach one or more chemical groups onto the filler to formthis type of modified filler can include any known attachment mechanismfor attaching chemical groups to filler particles, including diazoniumreactions.

The modified filler having attached chemical groups can be preparedusing and adapting the methods described in U.S. Pat. Nos. 5,554,739;5,707,432; 5,837,045; 5,851,280; 5,885,335; 5,895,522; 5,900,029;5,922,118; 6,042,643; 6,398,858; 7,175,946; 6,471,763; 6,780,389;7,217,405; 5,859,120; and 6,290,767; U.S. Patent Application PublicationNos. 2003-0129529 A1; 2002-0020318; 2002-0011185 A1; and 2006-0084751A1, and PCT Publication No. WO 99/23174, which are incorporated in theirentireties herein by reference. These references describe, in part, theuse of diazonium chemistry to attach functional groups to pigments. Asjust an example, these processes have been adapted and used to form themodified fillers of the present invention (having attached chemicalgroups).

An amino version of a triazole, pyrazole, and/or imidazole can be used(examples provided in the Example section of this application), and thenusing the diazonium reaction, for instance, described in the abovepatents, can be attached onto the filler to form this version of themodified filler having an attached chemical group, such as an organicgroup, and such as an attached at least one triazole group, pyrazolegroup, and/or imidazole group. The attached triazole, pyrazole, and/orimidazole group are further exemplified below for another version of amodified filler, and would be applicable here as well.

The modified filler (with attached chemical groups) may be preparedusing any method known to those skilled in the art for attachingchemical groups. For example, the modified fillers can be prepared usingthe methods described in the above cited patents/publications. Othermethods for preparing the modified fillers include reacting a fillerhaving available functional groups with a reagent comprising the organicgroup, such as is described in, for example, U.S. Pat. No. 6,723,783,which is incorporated in its entirety by reference herein. Suchfunctional fillers may be prepared using the methods described in thereferences incorporated above. In addition modified fillers containingattached functional groups may also be prepared by the methods describedin U.S. Pat. Nos. 6,831,194 and 6,660,075, U.S. Patent Publication Nos.2003-0101901 and 2001-0036994, Canadian Patent No. 2,351,162, EuropeanPatent No. 1 394 221, and PCT Publication No. WO 04/63289, as well as inN. Tsubokawa, Polym. Sci., 17, 417, 1992, each of which is alsoincorporated in their entirety by reference herein.

The amount of attached groups can be varied, depending on the desireduse of the modified filler and the type of attached group. For example,the total amount of organic group attached may be from about 0.01 toabout 6.0 micromoles of groups/m² surface area of filler, as measured bynitrogen adsorption (BET method), including from about 0.1 to about 5.0micromoles/m², from about 0.2 to about 3.0 micromoles/m², or from about0.3 to about 2.0 micromoles/m².

Examples of the triazole, pyrazole, and/or imidazole groups are the sameas for the adsorbed chemical groups described above, except these groupsare attached, for instance, by way of a chemical bond to the filler.Examples of the attached chemical groups are set forth below.

For purposes of the present invention, the triazole includes a chemicalgroup that has a triazole-containing group. The triazole can be a 1,2,4triazole or a 1,2,3 triazole. The triazole can be a thiol orpolysulfide-containing polytriazole. 1,2,4 triazole or 1,2,4triazole-containing groups are preferred as adsorbed and/or attachedtriazole chemical groups in view of achieved properties, especially inelastomeric composites. With regard to the attached triazole, examplesinclude, but are not limited to, the following:

or tautomers thereof,

wherein the substituents are the same as stated earlier, except X (orone of the X's) is or includes a bond to the filler to become attached.

In the triazole formulas,

Z_(b) is an alkylene group (e.g., a C₁-C₄ alkylene), where b is 0 or 1;

at least one X comprises a bond to the filler, and any remaining Xcomprises a bond to the filler or a functional group, such as thevarious substituents A and/or R described herein;

A is a functional group that is S_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′,SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), or2-(1,3-dithiolanyl); or a linear, branched, aromatic, or cyclichydrocarbon radical substituted with one or more of the functionalgroup(s);

where R and R′, which are the same or different, are hydrogen; branchedor unbranched C₁-C₁₂ unsubstituted or substituted alkyl, alkenyl,alkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; unsubstituted orsubstituted arylalkyl, arylene, heteroarylene, or alkylarylene;

k is an integer from 1 to 8 when R is H and otherwise k is 2 to 8;

Q is (CH₂)_(w), (CH2)_(x) O(CH₂)_(z), (CH₂)_(x) NR(CH₂)_(z), or(CH₂)_(x) S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6;

E is a polysulfur-containing radical; and

the triazole can be optionally N-substituted with an NDD′ substituent,where

D and D′, which are the same or different, are H or C₁-C₄ alkyl; and

Y is H, alkyl, aryl, or NH₂.

In specific examples, the group attached to the filler can be or includea mercapto-triazolyl group, e.g. a 5-mercapto-1,2,4-triazole-3-yl group,and/or a triazole disulfide group, and/or a 1,2,4-triazol-3-yl group.The group attached to the filler can be or include a2-mercapto-1,3,4-thiadiazol-5-yl group and/or a thiadiazole disulfidegroup. Substituted or unsubstituted oxadiazole groups as well as othersubstituted or unsubstituted azole, e.g., diazole, groups, can beattached, e.g., directly, to the filler.

For purposes of the present invention, the attached pyrazole is orincludes a chemical that has a pyrazole-containing group. The pyrazolecan be a thiol or polysulfide-containing polypyrazole. With regard tothe pyrazole, examples include, but are not limited to, the following:

or tautomers thereof,

wherein the substituents are the same as stated earlier, except X (orone of the X's) is or includes a bond to the filler to become attached.

In the pyrazole formulas,

Z_(b) is an alkylene group (e.g., a C₁-C₄ alkylene), where b is 0 or 1;

at least one X or Y comprises a bond to the filler and any other X or Y,which is the same or different, comprises a bond or a functional group,such as the various substituents A and/or R described herein;

A is a functional group that is S_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′,SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), or2-(1,3-dithiolanyl); or a linear, branched, aromatic, or cyclichydrocarbon radical substituted with one or more of the functionalgroup(s);

where R and R′, which are the same or different, are hydrogen; branchedor unbranched C₁-C₁₂ unsubstituted or substituted alkyl, alkenyl,alkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; unsubstituted orsubstituted arylalkyl, arylene, heteroarylene, or alkylarylene;

k is an integer from 1 to 8 when R is H and otherwise k is 2 to 8;

Q is (CH₂)_(w), (CH2)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6;and

E is a polysulfur-containing group.

For purposes of the present invention, the attached imidazole is orincludes a chemical that has an imidazole-containing group. Theimidazole can be a thiol or polysulfide-containing polyimidazole. Withregard to the imidazole, examples include, but are not limited to, thefollowing:

or tautomers thereof,

wherein the substituents are the same as stated earlier, except X (orone of the X's) is or includes a bond to the filler to become attached.

In the imidazole formulas,

Z_(b) is an alkylene group (e.g., a C₁-C₄ alkylene), where b is 0 or 1;

each X comprises a bond to the filler, H, alkyl (examples providedelsewhere apply here), aryl (examples provided elsewhere apply here), orNH₂, with the proviso that at least one X comprises a bond;

Y is H or NH₂;

A is a functional group that is S_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′,SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), or2-(1,3-dithiolanyl); or a linear, branched, aromatic, or cyclichydrocarbon radical substituted with one or more of said functionalgroup;

where R and R′, which can be the same or different, are hydrogen;branched or unbranched C₁-C₁₂ unsubstituted or substituted alkyl,alkenyl, alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl;unsubstituted or substituted arylalkyl, arylene, heteroarylene, oralkylarylene;

k is an integer from 1 to 8;

Q is (CH₂)_(w), (CH2)_(x) O(CH₂)_(z), (CH₂), NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6; and

E is a polysulfur-containing group.

The attached organic group can be or comprise an alkyl group or aromaticgroup having at least functional group that is R, OR, COR, COOR, OCOR, acarboxylate salt, halogen, CN, NR₂, SO₃H, a sulfonate salt, NR(COR),CONR₂, NO₂, PO₃H₂, a phosphonate salt, a phosphate salt N═NR, NR₃ ⁺X⁻,PR₃ ⁺X⁻, S_(k)R, SSO₃H, a SSO₃ ⁻ salt, SO₂NRR′, SO₂SR, SNRR′, SNQ,SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl)2-(1,3-dithiolanyl), SOR, or SO₂R, wherein R and R′, which are the sameor different, are independently hydrogen, branched or unbranched C₁-C₁₀₀substituted or unsubstituted, saturated or unsaturated hydrocarbon, andk is an integer that ranges from 1-8, and X⁻ is a halide or an anionderived from a mineral or organic acid, Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherew is an integer from 2 to 6 and x and z are independently integers from1 to 6.

The attached organic group can be or comprise an aromatic group having aformula AyAr—, wherein Ar is an aromatic radical and A is R, OR, COR,COOR, OCOR, a carboxylate salt, halogen, CN, NR₂, SO₃H, a sulfonatesalt, NR(COR), CONR₂, NO₂, PO₃H₂, a phosphonate salt, a phosphate saltN═NR, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SSO₃H, a SSO₃ ⁻ salt, SO₂NRR′, SO₂SR,SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl)2-(1,3-dithiolanyl), SOR, or SO₂R, wherein R and R′,which are the same or different, are independently hydrogen, branched orunbranched C₁-C₁₀₀ substituted or unsubstituted, saturated orunsaturated hydrocarbon, and k is an integer that ranges from 1-8, andX⁻ is a halide or an anion derived from a mineral or organic acid, Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where w is an integer from 2 to 6 and x and z areindependently integers from 1 to 6, and y is an integer from 1 to thetotal number of —CH radicals in the aromatic radical.

Ar can be or comprise a triazole group, Ar can be or comprise a pyrazolegroup, or Ar can be or comprise an imidazole group.

The attached organic group can be or comprise at least oneaminomethylphenyl group and/or carboxyphenyl.

The attached organic group can be or comprise X—C₆H₄—S—S—C₆H₄—X, whereat least one X is a bond to the filler and the other X is a bond to thefiller or a functional group, such as the substituent A describedherein.

The attached organic group can be or comprise at least one aromaticsulfide or polysulfide.

As an option, one or more additional but different chemical groups canbe attached onto the filler, such as one or more additional chemicalgroups that are different from an attached triazole, attached pyrazole,and/or attached imidazole. The attached chemical group can be any of theattached chemical groups described earlier and/or in the above-mentionedpatents, such as an attached alkyl group and/or attached aromatic group,for instance, amino methyl phenyl, carboxy phenyl, or phenyl disulfidephenyl (C₆H₅—S—S—C₆H₄).

For purposes of the present invention, a further version of the modifiedfillers of the present invention is where the modified filler comprisesa filler having attached at least one triazole, such as at least 1,2,4triazole, such as at least 1,2,4 triazole having a sulfur-containingsubstituent, for instance, in the presence or absence of any otheraromatic group. The modified filler having the attached chemical group,such as the at least one triazole, can improve hysteresis when presentin an elastomer composition compared to the same filler that is notmodified. Again, the elastomeric formulations set forth in the Examplescan be used to confirm this test property. A further modified filler ofthe present invention is or comprises a filler having attached thereon atriazole comprising:

or tautomers thereof, wherein

wherein Z_(b) is an alkylene group (e.g., a C₁-C₄ alkylene), where b is0 or 1;

at least one X comprises a bond to the filler and any remaining Xcomprises a bond to the filler or a functional group, such as thevarious substituents A or R described herein;

A is a functional group that is S_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′,SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), or2-(1,3-dithiolanyl); or a linear, branched, aromatic, or cyclichydrocarbon radical substituted with one or more of the functionalgroup(s);

where R and R′, which can be the same or different, are hydrogen;branched or unbranched C₁-C₁₂ unsubstituted or substituted alkyl,alkenyl, alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl;unsubstituted or substituted arylalkyl, arylene, heteroarylene, oralkylarylene;

k is an integer from 1 to 8;

Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂),S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6;

E is a polysulfur-containing radical; and

the triazole can be optionally N-substituted with an NDD′ substituent,where

D and D′, which are the same or different, are H or C₁-C₄ alkyl.

This version of the modified filler can be with or without any adsorbedchemical groups.

Throughout the present application, with respect to the attachedchemical groups onto the filler, the chemical group is attached throughat least one bond from the chemical group to the filler. In the presentapplication, the substituent X can represent or comprise a bond. It isto be understood for purposes of the present invention that thesubstituent X can include a bond, as well as other substituents orelements, for instance, for purposes of achieving the bond to thefiller. For example, X can be or consist of a bond. In the alternative,X can comprise a bond. For instance, X can be a bond that includes alinker group. The linker group can be a silane linker group or derivedfrom a silane coupling agent. The linker group can be or include aSi-containing group, a Ti-containing group, a Cr-containing group,and/or Zr-containing group, or other suitable linker groups that promotethe attachment of a chemical group onto a filler, such as a metal oxidefiller, for instance, silica. Examples of such linkers which can beadopted for purposes of the present invention, include those set forthin U.S. Pat. Nos. 3,947,436; 5,159,009; and 5,116,886, all incorporatedin their entirety by reference herein.

In the present invention, for the various versions (adsorbed and/orattached groups) of the modified filler of the present invention, thepreparation of the modified filler can occur and should occur prior tothe filler being introduced with other ingredients, such as theingredients to form an elastomeric composition, such as at least oneelastomer. Put another way, the chemical group(s) used in the presentinvention are pre-adsorbed and/or pre-attached to the filler(s) prior tomixing or compounding or otherwise contacting at least one elastomer orat least one polymer and/or other components of a formulation. Thepresent inventors have discovered that various properties achieved bythe present application, namely hysteresis and/or abrasion resistancecan be diminished or not achieved at all when the modification of thefiller is attempted in the presence of other ingredients (e.g., insitu), such as trying to compound with at least one elastomer and/or atleast one polymer.

For purposes of the present invention, any combination of modifiedfillers of the present invention can be used. For instance, as describedherein, various versions of the modified filler have been described. Forinstance, one version of the modified filler of the present invention isa filler having adsorbed groups and, optionally, with attached chemicalgroups. Another version of the present invention involves a fillerhaving attached chemical groups without any adsorbed groups. Thus, asone option, a formulation, such as an elastomeric formulation, cancomprise a combination of various modified fillers of the presentinvention, for instance, some modified filler having one or moreadsorbed chemical groups can be used in combination with one or moreother modified fillers having attached chemical groups. Thus, anycombination of the modified fillers in formulations, such as elastomericor polymeric formulations, can be used.

For purposes of the present invention, when the modified filler has anadsorbed chemical group and an attached chemical group, the placement ofthe adsorbed chemical group onto the filler can occur before, during,and/or after attachment of the chemical group, or in any sequence whenmore than one adsorbed and/or more than one attached group is present onthe filler.

The present invention further relates to elastomeric compositions orelastomeric composites, also considered rubber compositions orcomposites. The elastomeric composition contains at least one elastomerand at least one modified filler of the present invention and,optionally, one or more conventional components used in elastomerformulations. More than one type of modified filler can be used.

Exemplary elastomers include, but are not limited to, rubbers, polymers(e.g., homopolymers, copolymers and/or terpolymers) of 1,3-butadiene,styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene, where alkylmay be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propyleneand the like. The elastomer may have a glass transition temperature(Tg), as measured by differential scanning calorimetry (DSC), rangingfrom about −120° C. to about 0° C. Examples include, but are not limitedto, solution SBR, styrene-butadiene rubber (SBR), natural rubber and itsderivatives such as chlorinated rubber, polybutadiene, polyisoprene,poly(styrene-co-butadiene) and the oil extended derivatives of any ofthem. Blends of any of the foregoing may also be used. Particularsuitable synthetic rubbers include: copolymers of from about 10 to about70 percent by weight of styrene and from about 90 to about 30 percent byweight of butadiene such as copolymer of 19 parts styrene and 81 partsbutadiene, a copolymer of 30 parts styrene and 70 parts butadiene, acopolymer of 43 parts styrene and 57 parts butadiene and a copolymer of50 parts styrene and 50 parts butadiene; polymers and copolymers ofconjugated dienes such as polybutadiene, polyisoprene, polychloroprene,and the like, and copolymers of such conjugated dienes with an ethylenicgroup-containing monomer copolymerizable therewith such as styrene,methyl styrene, chlorostyrene, acrylonitrile, 2-vinyl-pyridine,5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine,2-methyl-5-vinylpyridine, allyl-substituted acrylates, vinyl ketone,methyl isopropenyl ketone, methyl vinyl either, alphamethylenecarboxylic acids and the esters and amides thereof such as acrylic acidand dialkylacrylic acid amide. Also suitable for use herein arecopolymers of ethylene and other high alpha olefins such as propylene,1-butene and 1-pentene. As noted further below, the rubber compositionscan contain, in addition to the elastomer and filler and coupling agent,various processing aids, oil extenders, antidegradents, and/or otheradditives.

As an option, a continuously-fed latex and a filler, such as a carbonblack slurry, can be introduced and agitated in a coagulation tank. Thisis also known as a “wet mix” technique. The latex and filler slurry canbe mixed and coagulated in the coagulation tank into small beads,referred to as “wet crumb.” The various processes and techniquesdescribed in U.S. Pat. Nos. 4,029,633; 3,048,559; 6,048,923; 6,929,783;6,908,961; 4,271,213; 5,753,742; and 6,521,691 can be used for thiscombination of filler with elastomer and coagulation of the latex. Eachof these patents are incorporated in their entirety by reference herein.This type of elastomeric formulation can be used with the modifiedfillers of the present invention using the various techniques,formulations, and other parameters described in these patents andprocesses, except that the modified fillers of the present invention areused.

Exemplary natural rubber latices include, but are not limited to, fieldlatex, latex concentrate (produced, for example, by evaporation,centrifugation or creaming), skim latex (e.g., the supernatant remainingafter production of latex concentrate by centrifugation) and blends ofany two or more of these in any proportion. The latex should beappropriate for the wet masterbatch process selected and the intendedpurpose or application of the final rubber product. The latex isprovided typically in an aqueous carrier liquid. Selection of a suitablelatex or blend of latices will be well within the ability of thoseskilled in the art given the benefit of the present disclosure and theknowledge of selection criteria generally well recognized in theindustry.

Elastomer composites can be prepared with a filler loading of at leastabout 40 phr, at least about 50 phr, at least about 55 phr, at leastabout 60 phr, at least about 65 phr, or at least about 70 phr of carbonblack, for example, from about 40 to about 70 phr, from about 50 toabout 75 phr, from about 55 to about 80 phr, from 60 to about 85 phr,from 65 to about 90 phr, from 70 to about 90 phr, from 40 to about 60phr, between 50 and about 65 phr, from 55 to about 80 phr, from about 60to about 90 phr, from about 65 to about 80 phr, or from about 70 toabout 80 phr.

One or more coupling agents can be used in the present invention. Thecoupling agent can be or include one or more silane coupling agents, oneor more zirconate coupling agents, one or more titanate coupling agents,one or more nitro coupling agents, or any combination thereof. Thecoupling agent can be or include bis(3-triethoxysilylpropyl)tetrasulfane(e.g., Si 69 from Evonik Industries, Struktol SCA98 from StruktolCompany), bis(3-triethoxysilylpropyl)disulfane (e.g., Si 75 and Si 266from Evonik Industries, Struktol SCA985 from Struktol Company),3-thiocyanatopropyl-triethoxy silane (e.g., Si 264 from EvonikIndustries), gamma-mercaptopropyl-trimethoxy silane (e.g., VP Si 163from Evonik Industries, Struktol SCA989 from Struktol Company),gamma-mercaptopropyl-triethoxy silane (e.g., VP Si 263 from EvonikIndustries), zirconium dineoalkanolatodi(3-mercapto) propionato-O,N,N′-bis(2-methyl-2-nitropropyl)-1,6-diaminohexane, NXT silane couplingagent (a thiocarboxylate functional silane:3-Octanoylthio-1-propyltriethoxysilane) from Momentive PerformanceMaterials, Wilton, Conn., and/or coupling agents that are chemicallysimilar or that have the one or more of the same chemical groups.Additional specific examples of coupling agents, by commercial names,include, but are not limited to, VP Si 363 from Evonik Industries. Thecoupling agent can be present in any amount in the elastomer composite.For instance, the coupling agent can be present in the elastomercomposite in an amount of at least 0.2 parts per hundred parts offiller, such as silica (by mass), from about 0.2 to 60 parts per hundredof filler, such as silica, from about 1 to 30 parts per hundred offiller, such as silica, from about 2 to 15 parts per hundred of filler,such as silica, or from about 5 to 10 parts per hundred of filler, suchas silica.

One or more antioxidants can be used in any of the processes of thepresent invention. The antioxidant (an example of a degradationinhibitor) can be an amine type antioxidant, phenol type antioxidant,imidazole type antioxidant, metal salt of carbamate, para-phenylenediamine(s) and/or dihydrotrimethylquinoline(s), polymerized quinineantioxidant, and/or wax and/or other antioxidants used in elastomerformulations. Specific examples include, but are not limited to,N-(1,3-dimethylbutyl)-N-phenyl-p-phenylenediamine (6-PPD, e.g., ANTIGENE6C, available from Sumitomo Chemical Co., Ltd. and NOCLAC 6C, availablefrom Ouchi Shinko Chemical Industrial Co., Ltd.), “Ozonon” 6C from SeikoChemical Co., Ltd., polymerized 1,2-dihydro-2,2,4-trimethyl quinoline,Agerite Resin D, available from R. T. Vanderbilt, butylhydroxytoluene(BHT), and butylhydroxyanisole (BHA), and the like. Other representativeantioxidants may be, for example, diphenyl-p-phenylenediamine and otherssuch as, for example, those disclosed in The Vanderbilt Rubber Handbook(1978), pages 344-346, which is incorporated in its entirety byreference herein. An antioxidant and an antiozonate are collectivelydegradation inhibitors. These degradation inhibitors illustrativelyinclude a chemical functionality, such as an amine, a phenol, animidazole, a wax, a metal salt of an imidazole, and combinationsthereof. Specific degradation inhibitors operative herein illustrativelyinclude N-isopropyl-N-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N-phenyl-p-phenylenediamine,6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline,N,N′-diphenyl-p-phenylenediamine, octylated diphenylamine,4,4′-bis(a,a′-dimethylbenzyl)diphenylamine, 4,4′-dicumyl-diphenylamine,2,5-di-tert-butyl-hydroquinone,2,2′-methylene-bis(4-methyl-6-tert-butylphenol),2,2′-methylenebis(4-methyl-6-methylcyclohexlphenol),4,4′-thio-bis(3-methyl-6-tert-butylphenol),4,4′-butylidene-bis(3-methyl-6-tert-butylphenol), tris(nonylatedphenyl)phosphite, tris-(2,4-di-t-butylphenyl)phosphite,2-mercaptobenzimidazole, and zinc 2-mercaptobenzimidazole. An exampleincludes at least one amine and one imidazole. Optionally, a polymerizedquinoline can be used. The relative amounts of antioxidants can include0.5 to 3 parts amine, 0.5 to 2.5 parts imidazole, and 0.5 to 1.5 partsof optional polymerized quinoline. The degradation inhibiting amine canbe 4,4′-bis(alpha-dimethylbenzyl)diphenylamine, the imidazole can bezinc 2-mercaptotoluimidazole and the polymerized quinoline can bepolymerized 1,2-dihydro-2,2,4-trimethylquinoline. In general, thedegradation inhibitors (e.g., the antioxidant(s)) are typically presentfrom 0.1 to 20 parts by weight per 100 parts by weight of polymer orrubber system (phr). Typical amounts of antioxidants may comprise, forexample, from about 1 to about 5 phr.

The rubber composition can be for tire or tire parts and can utilize ahydrophilic filler. The hydrophilic filler can have an organic groupattached to the filler and the organic group is or includes asubstituted or unsubstituted azole group. The group can be a triazole,e.g., a mercapto-triazole and/or a triazole disulfide. The group can bea thiadiazole, e.g., a thiol-substituted thiadiazole.

The modified filler can be combined with conventional tire compoundingredients and additives, such as rubbers, processing aids,accelerators, cross-linking and curing materials, antioxidants,antiozonants, fillers, resins, etc. to make tire compounds. Processingaids include, but are not limited to, plasticizers, tackifiers,extenders, chemical conditioners, homogenizing agents, and peptizerssuch as mercaptans, synthetic oil, petroleum and vegetable oils, resins,rosins, and the like. Accelerators include amines, guanidines,thioureas, thiurams, sulfenamides, thiocarbamates, xanthates,benzothiazoles and the like. Cross-linking and curing agents includeperoxides, sulfur, sulfur donors, accelerators, zinc oxide, and fattyacids. Fillers include clay, bentonite, titanium dioxide, talc, calciumsulfate, silica, silicates and mixtures thereof.

Any conventional mixing procedure can be used to combine the modifiedfiller of the present invention with other components of an elastomercomposite. Typical procedures used for rubber compounding are describedin Maurice Morton, RUBBER TECHNOLOGY 3^(rd) Edition, Van NorstrandReinhold Company, New York 1987, and 2^(nd) Edition, Van NordstrandReinhold Company, New York 1973. The mixture of components includingmodified carbon black product of the present invention and an elastomeris preferably thermomechanically mixed together at a temperature between120° C. and 180° C.

For example, elastomeric composites of the present invention can beobtained by suitable techniques that employ, for instance, mixing in asingle step or in multiple steps in an internal mixer, such as aBanbury, Intermesh mixers, extruder, on a mill or by utilizing othersuitable equipment, to produce a homogenized blend. Specificimplementations use techniques such as those described in U.S. Pat. No.5,559,169, published Sep. 24, 1996 which is incorporated herein byreference in its entirety.

Curing can be conducted by techniques known in the art. For example, themodified fillers of the present invention can be used in rubbercompositions which are sulfur-cured, peroxide-cured and so forth.

The modified filler(s) of the present invention can improve one or moreelastomeric properties, such as hysteresis and/or abrasion resistance.Improvement in hysteresis can be measured by measuring the tan/deltaproperties.

The abrasion index is the ratio of the abrasion rate of an internalcontrol composition divided by the abrasion rate of a rubber compositionprepared with a modified filler of the present invention. Forsimplicity, relative abrasion index values are used in the examplesbelow. The relative abrasion index is defined as the ratio of abrasionindex of rubber compositions with the modified filler of the presentinvention divided by the abrasion index of rubber compositions withuntreated filler. In examples where the modified fillers of the presentinvention are used in combination with other treatments, relativeabrasion index is defined as the ratio of abrasion index of rubbercompositions with modified filler of the present invention used incombination with a second treatment divided by the abrasion index ofrubber compositions with filler treated with the same second treatment.It is generally desirable in the production of tire treads to utilizefillers which produce tire treads with satisfactory abrasion resistanceand/or reduced rolling resistance. Typically, the tread wear propertiesof a tire are related to this abrasion resistance. The greater theabrasion resistance, the greater the number of miles the tire will lastwithout wearing out. Abrasion data on rubber compositions can bedetermined using an abrader based on a Lambourn type machine (see, forinstance, U.S. Pat. No. 4,995,197). Abrasion rates (cubiccentimeter/centimeter travel) typically are measured at 14% or 21% slip,the slip being based on the relative velocity between the sample wheeland grindstone.

It has also been discovered that the modified filler of the presentinvention can improve hysteresis, for instance, shown by a lowerrelative maximum tan δ (delta) values in comparison to untreated filler.Lower relative maximum tan δ (delta) values are desirable as theyreflect reduced rolling resistance and reduced heat build up in thetread portion of a tire. Reduced rolling resistance improves fueleconomy of the car and is a desirable attribute of an elastomercomposite for use in the tread portion of a tire.

Tan δ was measured with a Rheometrics Dynamic Spectrometer Model ARES-2Kat a constant frequency of 10 Hz, a constant temperature, and in shearmode of strain. Strain sweeps were run from 0.1% to 60% double strainamplitude. Measurements were taken at ten points per decade and themaximum measured tan δ was reported. Relative maximum tan δ value isdefined as the ratio of measured maximum tan δ for rubber compositionswith modified filler of the present invention divided by the maximum tanδ of rubber compositions with untreated filler. In examples where themodified fillers of the present invention are used in combination withother treatments, relative maximum tan δ is defined as the ratio ofmeasured maximum tan δ for rubber compositions with modified filler ofthe present invention used in combination with a second treatmentdivided by the measured maximum tan δ for rubber compositions withfiller treated with the same second treatment.

In the present invention, a modified filler, which can be a fillerhaving an adsorbed chemical group as described herein, has the abilityto improve abrasion resistance in an elastomeric composition and thiscan be compared to when an elastomer composition contains the samefiller, but is unmodified. Put another way, two elastomeric compositionscan be formed—one containing the modified filler of the presentinvention, which is a filler A modified to have an adsorbed chemicalgroup and this can be compared to the same filler A, but not modifiedwith any adsorbed chemical group (e.g., an unmodified filler A). Whenthis comparison is made, the modified filler of the present invention,which is present in the elastomeric composition, can improve abrasionresistance. For instance, the abrasion resistance can be increased by atleast 5%, at least 10%, at least 30%, at least 50%, at least 60%, atleast 70%, at least 75%, at least 85%, at least 100%, at least 125%, atleast 150%, at least 200%, such as from 5% to 200%, compared to theunmodified filler.

In the present invention, a modified filler, which can be a fillerhaving an attached chemical group as described herein, has the abilityto improve hysteresis in an elastomeric composition and this can becompared to when an elastomer composition contains the same filler, butis unmodified. Put another way, two elastomeric compositions can beformed—one containing the modified filler of the present invention,which is a filler B modified to have an attached chemical group and thiscan be compared to the same filler B, but not modified with any attachedchemical group (e.g., an unmodified filler B). When this comparison ismade, the modified filler of the present invention, which is present inthe elastomeric composition, can improve hysteresis. For instance, thehysteresis can be decreased by at least 1%, at least 5%, at least 10%,at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, atleast 40%, at least 45%, or at least 50%, such as from 1% to 50%,compared to the unmodified filler.

The benefits mentioned above with regard to abrasion resistance andhysteresis can be achieved at the same time in the present invention orcan be individually controlled. More specifically, the hysteresis can beimproved (decreased) and abrasion resistance increased by the use of amodified filler that has an adsorbed chemical group as described hereinand an attached chemical group as described herein. Examples of the typeof improvements achieved with respect to hysteresis and abrasionresistance (namely the percent improvement mentioned earlier) can beachieved in combination, and any combination of the various percents forhysteresis and abrasion resistance mentioned above can be achieved.

The modified fillers of the present invention can be used in the sameapplications as conventional fillers, such as inks, coatings, toners,plastics, cable, and the like.

The present invention will be further clarified by the followingexamples, which are intended to be exemplary of the present invention.

EXAMPLES Example 1 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 2.60 g NaNO2 in 21.7 g ofwater was added over a period of about five minutes to a stirringmixture of 150 g of the carbon black, 1301 g water, 5.00 g3-amino-1,2,4-triazole-5-thiol and 5.14 g 70% methanesulfonic acid at 70C. The mixing was continued for 50 minutes at 70 C. The mixture wascooled to room temperature and adjusted to a pH of 8.1 with NaOHsolution. The product was collected by filtration, washed with 2.5 L ofwater and dried under vacuum at 70 C. The product had 1.53 wt % S. Asample of the carbon black product that had been subjected to Soxhletextraction with methanol had 0.89 wt % S, compared to 0.65 wt % S forthe untreated carbon black. The sample thus had attached and adsorbedtriazoles.

Example 2 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 2.61 g NaNO2 in 23.1 g ofwater was added over a period of ten minutes to a stirring mixture of150 g of the carbon black, 1301 g water, 4.31 g3-amino-1,2,4-triazole-5-thiol and 5.14 g 70% methanesulfonic acid at 70C. The mixing was continued for an hour at 70 C. The mixture was cooledto room temperature and adjusted to a pH of 7.5 with NaOH solution. Theproduct was collected by filtration, washed with 2.5 L of water anddried under vacuum at 70 C. The product had 1.41 wt % S. A sample of thecarbon black product that had been subjected to Soxhlet extraction withmethanol had 0.89 wt % S, compared to 0.65 wt % S for the untreatedcarbon black. The sample thus had attached and adsorbed triazoles.

Example 3 Preparation of a Comparative Carbon Black Product

This example illustrates the preparation of a carbon black productmodified using diazonium salts of APDS. A batch pelletizer having amixing chamber with a 8″ diameter and 8″ length was heated to 60 C. andcharged with 300 g of a carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g. 4-Aminophenyldisulfide (19.0 g) and 209 g of waterwere added. After mixing briefly, 29.0 g of 27.9% sulfuric acid wasadded. After mixing briefly, 52 g of a 20% solution of NaNO2 in waterwas added in a few portions, with brief intermediate mixing over fiveminutes. Water (50 g) was added, and mixing was continued for 30 min at60 C, and the product was removed from the pelletizer, suspended in 4 Lwater and filtered. The product was washed with ethanol and thenresuspended in 4 L of water. The pH was adjusted to 8 with NaOHsolution, and the mixture was filtered and washed until the filtrate hada conductivity of 225 μS/cm. The product was dried in air at 70 C. Asample of the carbon black product that had been subjected to Soxhletextraction with methanol had 1.61 wt % S, compared to 0.60 wt % S forthe untreated carbon black.

Example 4 Preparation of a Comparative Carbon Black Product

This example illustrates the preparation of a carbon black productmodified using diazonium salts of ATP. A batch pelletizer having amixing chamber with a 8″ diameter and 8″ length was heated to 60 C. andcharged with 300 g of a carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g. 4-Aminothiophenol (9.67 g) and 240 g of water wereadded. After mixing briefly, 14.5 g of 27.9% sulfuric acid was added.After mixing briefly, 26 g of a 20% solution of NaNO2 in water was addedin a few portions, with brief intermediate mixing over five minutes.Water (50 g) was added, and mixing was continued for 30 min at 60 C, andthe product was removed from the pelletizer, suspended in 4 L water andfiltered. The product was resuspended in 4 L of water. The pH wasadjusted to 9 with NaOH solution, and the mixture was filtered andwashed until the filtrate had a conductivity of less than 250 μS/cm. Theproduct was dried in air at 70 C. A sample of the carbon black productthat had been subjected to Soxhlet extraction with methanol had 1.09 wt% S, compared to 0.60 wt % S for the untreated carbon black.

Example 5 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A solution of 1.29 g NaNO2 in 11.9 g of water wasadded over a period of five minutes to a stirring mixture of 150 g ofIntermediate Sample X, 1301 g water, 2.17 g3-amino-1,2,4-triazole-5-thiol and 2.58 g 70% methanesulfonic acid at 70C. The mixing was continued for 75 minutes at 70 C. The mixture wascooled to room temperature and adjusted to a pH of 7.5 with NaOHsolution. The product was collected by filtration, washed with 2.5 L ofwater and dried under vacuum at 70 C. The product had 1.07 wt % S. Asample of the carbon black product that had been subjected to Soxhletextraction with methanol had 0.80 wt % S, compared to 0.65 wt % S forthe untreated carbon black. The sample thus had attached and adsorbedtriazoles.

Example 6 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A suspension of 1300 g water, 150 g carbon blackand 100 g Clorox sodium hypochlorite solution was mixed and heated to 90C. The carbon black had an iodine number of 119 and a DBPA of 125 mL/100g. Mixing was continued for 70 minutes, and the suspension was cooled to70 C. The pH was adjusted to 4.9 with 0.166 g concentrated H2SO4.3-Amino-1,2,4-triazole-5-thiol (4.32 g) and 5.15 g 70% methanesulfonicacid were added. A solution of 2.60 g NaNO2 in 21.6 g of water was addedover a period of ten minutes. The mixing was continued for 65 minutes at70 C. The mixture was cooled to room temperature and adjusted to a pH of7.6 with NaOH solution. The product was collected by filtration, washedwith 2 L of water and dried under vacuum at 70 C. The product had 1.38wt % S. A sample of the carbon black product that had been subjected toSoxhlet extraction with methanol had 0.87 wt % S, compared to 0.65 wt %S for the untreated carbon black. The sample thus had attached andadsorbed triazoles.

Example 7 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 1.30 g NaNO2 in 12.0 g ofwater was added over a period of six minutes to a stirring mixture of150 g of the carbon black, 1300 g water, 2.16 g3-amino-1,2,4-triazole-5-thiol and 2.58 g 70% methanesulfonic acid at 70C. The mixing was continued for an hour at 70 C. Sulfanilic acid (6.49g) was added, and then a solution of 2.59 g NaNO2 in 22.3 g water wasadded over five minutes. The mixing was continued for an hour at 70 C.The mixture was cooled to room temperature and adjusted to a pH of 7.5with an aqueous NaOH solution. The product was collected and washed withmethanol using a Millipore pressure filter having a 0.45 micronmembrane. The resulting dispersion was dried at 70 C. A sample of thecarbon black product that had been subjected to Soxhlet extraction withmethanol had 1.37 wt % S and 0.58 wt % N compared to 0.65 wt % S and0.34 wt % N for the untreated carbon black.

Example 8 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 2.62 g NaNO2 in 21.8 g ofwater was added over a period of 15 minutes to a stirring mixture of 150g of the carbon black, 1301 g water, 4.31 g3-amino-1,2,4-triazole-5-thiol and 5.15 g 70% methanesulfonic acid at 70C. The mixing was continued for 65 minutes at 70 C. Sulfanilic acid(6.49 g) was added, and then a solution of 2.59 g NaNO2 in 23.1 g waterwas added over about ten minutes. The mixing was continued for an hourat 70 C. The mixture was cooled to room temperature and adjusted to a pHof 7.5 with an aqueous NaOH solution. The product was collected, washedwith 50/50 water/methanol and then washed with methanol using aMillipore pressure filter having a 0.45 micron membrane. The resultingdispersion was dried at 70 C. A sample of the carbon black product thathad been subjected to Soxhlet extraction with methanol had 1.31 wt % Sand 0.64 wt % N compared to 0.65 wt % S and 0.34 wt % N for theuntreated carbon black.

Example 9 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 2.60 g NaNO2 in 22.4 g ofwater was added over a period of ten minutes to a stirring mixture of150 g of the carbon black, 1301 g water, 4.31 g3-amino-1,2,4-triazole-5-thiol and 5.16 g 70% methanesulfonic acid at 70C. The mixing was continued for an hour at 70 C. Sulfanilic acid (3.24g) was added, and then a solution of 1.32 g NaNO2 in 11.7 g water wasadded over four minutes. The mixing was continued for an hour at 70 C.The mixture was cooled to room temperature and neutralized with anaqueous NaOH solution. The product was collected and washed withmethanol using a Millipore pressure filter having a 0.45 micronmembrane. The resulting dispersion was dried under vacuum at 70 C. Asample of the carbon black product that had been subjected to Soxhletextraction with methanol had 1.24 wt % S and 0.62 wt % N compared to0.65 wt % S and 0.34 wt % N for the untreated carbon black.

Example 10 Preparation of a Silicon Treated Carbon Black Product

This example illustrates the preparation of a silicon treated carbonblack product of the present invention. A silicon treated carbon blackwith an iodine number of 113, a STSA of 128 m2/g, a DBPA of 107 mL/100g, and a silicon content of 2.64 wt % was used. A solution of 2.60 gNaNO2 in 22.4 g of water was added over a period of ten minutes to astirring mixture of 150 g of the silicon treated carbon black, 1305 gwater, 4.32 g 3-amino-1,2,4-triazole-5-thiol, and 5.16 g 70%methanesulfonic acid at 70 C. The mixing was continued for 65 minutes at70 C. The mixture was cooled to room temperature and adjusted to a pH of7.5 with NaOH solution. The product was collected by filtration, washedwith 2 L of water and dried under vacuum at 70 C. The product had 1.04wt % S. A sample of the silicon-treated carbon black product that hadbeen subjected to Soxhlet extraction with methanol had 0.54 wt % S,compared to 0.35 wt % S for the untreated carbon black. The sample thushad attached and adsorbed triazoles.

Example 11 Preparation of a Silicon Treated Carbon Black Product

This example illustrates the preparation of a silicon treated carbonblack product of the present invention. A suspension of 1300 g water,150 g silicon treated carbon black and 100 g Clorox sodium hypochloritesolution was mixed and heated to 90 C. A silicon treated carbon blackwith an iodine number of 113, a STSA of 128 m2/g, a DBPA of 107 mL/100g, and a silicon content of 2.64 wt % was used. Mixing was continued for65 minutes, and the suspension was cooled to 70 C. The pH was adjustedto 5.1 with 0.042 g concentrated H2SO4. 3-Amino-1,2,4-triazole-5-thiol(4.32 g), and 5.17 g 70% methanesulfonic acid were added. A solution of2.62 g NaNO2 in 22.1 g of water was added over a period of ten minutes.The mixing was continued for an hour at 70 C. The mixture was cooled toroom temperature and adjusted to a pH of 7.6 with NaOH solution. Theproduct was collected by filtration, washed with 2.5 L of water anddried under vacuum at 70 C. The product had 1.00 wt % S. A sample of thecarbon black product that had been subjected to Soxhlet extraction withmethanol had 0.54 wt % S, compared to 0.35 wt % S for the untreatedcarbon black. The sample thus had attached and adsorbed triazoles.

Example 12 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 2.60 g NaNO2 in 22.5 g ofwater was added over a period of ten minutes to a stirring mixture of150 g of the carbon black, 1300 g water, 4.33 g3-amino-1,2,4-triazole-5-thiol and 5.14 g 70% methanesulfonic acid at 70C. The mixing was continued for an hour at 70 C. The mixture was cooledto room temperature and adjusted to a pH of 7.5 with NaOH solution. Theproduct was collected by filtration and washed with 2.5 L of water. Theproduct was combined with two additional batches made in substantiallythe same way. A portion of this mixture was dried under vacuum at 70 Cand used for Example 26. The product had 1.49 wt % S. A sample of thecarbon black product that had been subjected to Soxhlet extraction withmethanol had 0.88 wt % S, compared to 0.65 wt % S for the untreatedcarbon black. The sample thus had attached and adsorbed triazoles.

Example 13 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 3.91 g NaNO2 in 35.0 g ofwater was added over a period of five minutes to a stirring mixture of150 g of the carbon black, 1299 g water, 4.31 g3-amino-1,2,4-triazole-5-thiol and 7.71 g 70% methanesulfonic acid at 70C. The mixing was continued for an hour at 70 C. The mixture was cooledto room temperature and adjusted to a pH of 7.5 with NaOH solution. Theproduct was collected by filtration, washed with 2.5 L of water anddried under vacuum at 70 C. The product had 1.45 wt % S. A sample of thecarbon black product that had been subjected to Soxhlet extraction withmethanol had 1.03 wt % S, compared to 0.65 wt % S for the untreatedcarbon black. The sample thus had attached and adsorbed triazoles.

Example 14 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 5.21 g NaNO2 in 46.8 g ofwater was added over a period of ten minutes to a stirring mixture of150 g of the carbon black, 1300 g water, 4.32 g3-amino-1,2,4-triazole-5-thiol and 10.3 g 70% methanesulfonic acid at 70C. The mixing was continued for an hour at 70 C. The mixture was cooledto room temperature and adjusted to a pH of 7.6 with NaOH solution. Theproduct was collected by filtration, washed with 2.5 L of water anddried under vacuum at 70 C. The product had 1.38 wt % S. A sample of thecarbon black product that had been subjected to Soxhlet extraction withmethanol had 1.30 wt % S, compared to 0.65 wt % S for the untreatedcarbon black. The sample thus had attached and adsorbed triazoles.

Comparative Example A

This material is the carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g used in Examples 1-9.

Intermediate Sample X

A Process All 4HV mixer (4 L) was charged with 600 g of a carbon blackwith an iodine number of 119 and a DBPA of 125 mL/100 g. The materialwas mixed for ten minutes and heated to 55-75 C. Aqueous hydrogenperoxide solution (30%, 675 g) was added over 20 min. Mixing wascontinued for an additional 30 minutes at 75 C. The product was driedovernight in air at 130 C.

Comparative Example B

A 150 g portion of Intermediate Sample X was mixed with 1300 g water.The pH was adjusted to 7.7 with aqueous NaOH solution, filtered anddried under vacuum at 70 C.

Comparative Example C

A suspension of 1302 g water, 150 g carbon black and 100 g Clorox sodiumhypochlorite solution was mixed and heated to 90 C. The carbon black hadan iodine number of 119 and a DBPA of 125 mL/100 g. Mixing was continuedfor an hour, and the suspension was cooled to room temperature. The pHwas adjusted to 7.5 with aqueous NaOH. The product was collected byfiltration, washed with 2.5 L of water and dried under vacuum at 70 C.

Comparative Example D

A solution of 2.62 g NaNO2 in 22.3 g of water was added over a period often minutes to a stirring mixture of 150 g of the carbon black, 1300 gwater and 6.49 g sulfanilic acid at 70 C. A carbon black with an iodinenumber of 119 and a DBPA of 125 mL/100 g was used. The mixing wascontinued for an hour at 70 C. The mixture was cooled to roomtemperature and adjusted to a pH of 7.4 with an aqueous NaOH solution.The product was subjected to diafiltration until the conductivity of theeffluent was 350 μS/cm. The resulting dispersion was dried under vacuumat 70 C. A sample of the carbon black product that had been subjected toSoxhlet extraction with methanol had 1.00 wt % S, compared to 0.65 wt %S for the untreated carbon black.

Comparative Example E

This material is a silicon treated carbon black with an iodine number of113, a STSA of 128 m2/g, a DBPA of 107 mL/100 g, and a silicon contentof 2.64 wt %.

Comparative Example F

A suspension of 1300 g water, 150 g silicon treated carbon black and 100g Clorox sodium hypochlorite solution was mixed and heated to 90 C. Asilicon treated carbon black with an iodine number of 113, a STSA of 128m2/g, a DBPA of 107 mL/100 g, and a silicon content of 2.64 wt % wasused. Mixing was continued for an hour, and the suspension was cooled toroom temperature. The pH was adjusted to 7.5 with aqueous NaOH. Theproduct was collected by filtration, washed with 2 L of water and driedunder vacuum at 70 C.

Comparative Example G

A suspension of 901 g methanol, 150 g carbon black, and 4.32 g3-Amino-1,2,4-triazole-5-thiol was mixed for ten minutes. A carbon blackwith an iodine number of 119 and a DBPA of 125 mL/100 g was used. Thesolvent was removed with a rotary evaporator and the product was driedunder vacuum at 70 C.

Performance Characteristics of Elastomeric Composites

The composition of elastomeric composites prepared using carbon black orcarbon black product prepared according to the Examples above are shownin Tables A and B below. In all examples, unless specified otherwise,numerical values represent parts by weight.

The elastomer composites used herein were prepared by mixing Duradene™739 polymer with carbon blacks or carbon black products. Duradene™ 739polymer (Firestone Polymers, Akron Ohio) is a solution polymerizedstyrene-butadiene copolymer with 20% styrene and 60% vinyl butadiene.The components used in elastomer composites were mixed following atwo-stage mixing in Brabender Plasti-corder EPL-V mixer first at a rotorspeed of 60 rpm and starting temperature of 80 C followed by theaddition of curatives (sulfur ASTM QA purchased from Valasske Mezirici,Czech Republic; Santocure CBS and Perkacit MBT purchased from Solutia,Incorporated St. Louis, Mo.) in the second stage at a rotor speed of 50rpm and a starting temperature of 50 C. The components in first-stagewere mixed for a total of 5 minutes before passing through the open millthree times. The milled compound from first-stage mixing was kept atroom temperature for at least 2 h before second stage mixing. Thecuratives were then mixed in the second stage for 2 minutes.

TABLE A Example 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Duradene 739100 100 100 100 100 100 100 100 100 100 100 100 100 100 Carbon product50 example 1 Carbon product 50 example 2 Carbon product 50 example 3Carbon product 50 example 4 Carbon product 50 example 5 Carbon product50 example 6 Carbon product 50 example 7 Carbon product 50 example 8Carbon product 50 example 9 Carbon product 50 example 10 Carbon product50 example 11 Carbon product 50 example 12 Carbon product 50 example 13Carbon product 50 example 14 Zinc Oxide 3 3 3 3 3 3 3 3 3 3 3 3 3 3(ASTM) QA Stearic Acid 2 2 2 2 2 2 2 2 2 2 2 2 2 2 (ASTM) QA Santoflex 11 1 1 1 1 1 1 1 1 1 1 1 1 6PPD Sulfur 1.75 1.75 1.75 1.75 1.75 1.75 1.751.75 1.75 1.75 1.75 1.75 1.75 1.75 (ASTM) QA Santocure CBS 1.25 1.251.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 Perkacit MBT0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Total 159 159159 159 159 159 159 159 159 159 159 159 159 159

TABLE B Example 29 30 31 32 33 34 35 36 Duradene 739 100 100 100 100 100100 100 100 Comparative carbon example A 50 50 Comparative carbonexample B 50 Comparative carbon example C 50 Comparative carbon exampleD 50 Comparative carbon example E 51 Comparative carbon example F 51Comparative carbon example G 50 3-amino, 12,4-triazole, 5-thiol 1.45Bis(triethoxysilylpropyl) polysulfide 2 2 Zinc Oxide (ASTM) QA 3 3 3 3 33 3 3 Stearic Acid (ASTM) QA 2 2 2 2 2 2 2 2 Santoflex 6PPD 1 1 1 1 1 11 1 Sulfur (ASTM) QA 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 SantocureCBS 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 Perkacit MBT 0.2 0.2 0.2 0.20.2 0.2 0.5 0.2 Total 159 159 159 159 162 162 160 161

Shown in Table I are performance results (relative tan delta andrelative abrasion indices at 14% and 21% slip for elastomeric compositesthat include carbon black products (Examples 15 and 16 of the presentinvention) in comparison with untreated carbon black (Example 29).

TABLE I Relative Relative Relative maximum abrasion index abrasion indexExample tan delta at 14% slip at 21% slip 29 100 100 100 15 78 188 14016 92 218 160

Both samples that included modified carbon black (Examples 15 and 16)showed improved (lower) relative maximum tan delta values and increasedrelative abrasive indices. As discussed above, lower relative maximumtan delta values are desirable, as they reflect reduced heat build up inthe elastomer composite when subjected to cyclic strain. A higherrelative abrasive index also is desirable and reflects improved abrasionresistance.

In contrast to results obtained using diazonium salts of ATT, the datain Table II pertains to the performance of elasomeric composites thatemployed a carbon black product modified using diazonium salts ofpreviously disclosed, phenyl-containing agents: 4,4-aminophenyldisulfide(APDS), or 4-aminothiophenol (ATP). Table II also shows performance datafor untreated carbon.

TABLE II Relative Relative Relative maximum abrasion at abrasion atExample tan delta 14% slip 21% slip 29 100 100 100 17 72 65 86 18 85 7087

Examination of the data presented in Table I and in Table II reveals aconsiderable improvement in abrasion resistance for carbon black productderived from the diazonium salt of ATT compared to the performance ofmaterials derived from previously known treating agents, whilemaintaining similar improvements in tan delta. This is believed to beaccomplished by the attachment and adsorbing of triazole groups to thefiller.

Several experiments were undertaken to investigate performance ofelastomeric composites that included carbon black product obtained byusing ATT in combination with other treatments.

Table III, for example, shows comparison data for carbon blackperoxidized with hydrogen peroxide with or without ATT modification:

TABLE III Relative Relative Relative maximum abrasion index abrasionindex Example tan delta at 14% slip at 21% slip 30 100 100 100 19 84 116131

Table IV shows comparison data for carbon black peroxidized with sodiumhypochloride, with or without ATT modification:

TABLE IV Relative Relative Relative maximum abrasion index abrasionindex Example tan delta at 14% slip at 21% slip 31 100 100 100 20 72 7671

Results for elastomeric composites prepared using carbon black treatedwith the diazonium salt of sulfanilic acid, with or without ATT areshown in Table V:

TABLE V Relative Relative Relative maximum abrasion index abrasion indexExample tan delta at 14% slip at 21% slip 32 100 100 100 21 90 98 100 2286 106 107 23 79 128 127

Data for elastomeric composites that employed a starting material thatwas a dual phase silicon-containing filler (i.e., silicon-treated carbonblack) or a preoxidized silicon-containing filler, are shown in TablesVI-A and VI-B, respectively.

TABLE VI-A Relative Relative Relative maximum abrasion index abrasionindex Example tan delta at 14% slip at 21% slip 33 100 100 100 24 88 103109

TABLE VI-B Relative Relative Relative maximum abrasion index abrasionindex Example tan delta at 14% slip at 21% slip 34 100 100 100 25 78 228193

In all cases, the carbon products made from the diazonium salt of ATThad lower tan delta values than the controls. In some cases, modest tostrong improvements in wear resistance were found as well.

Experiments also were conducted to compare elastomeric composites thatused carbon black product that had the attached triazole group obtainedby using diazonium salts of ATT with elastomeric compositions in whichATT is not attached but rather it is physically mixed with carbon blackduring compounding with rubber, as described in U.S. Pat. No. 6,014,998.Table VII shows performance data obtained using carbon black productsprepared according to Examples 12, 13 and 14 as well as carbon blacksfrom comparative Examples A and G.

Examination of the results presented in Table VII clearly demonstratesthat attachment to the carbon black surface according to embodimentsdisclosed herein (e.g., Examples 26, 27 and 28) specifically improvesthe desired performance attributes. Furthermore, these Examples showthat the attachment level is an important parameter that can be variedto achieve optimal performance in the elastomer composite. Compoundsprepared from a carbon black with physically adsorbed ATT (Example 35)showed improvement with abrasion resistance. Results from untreatedcarbon black with ATT addition during compounding (Example 36) wereinferior to those made with carbon black products of the presentinvention.

TABLE VII Relative Relative Relative maximum abrasion index abrasionindex Example tan delta at 14% slip at 21% slip 29 100 100 100 26 94 168145 27 65 185 160 28 72 185 157 35 98 114 109 36 99 90 94

Example 37 Preparation of 3-amino-1,2,4-triazol-5-yl disulfide

Glacial acetic acid (2.60 g) was added to 4.89 g of a 15% aqueoushydrogen peroxide solution. The resulting solution was added over 20minutes to a solution prepared from 5.01 g3-amino-1,2,4-triazole-5-thiol, 65.2 g of water and 4.33 g 40% NaOH. Thereaction mixture was kept between 18 C-22 C by use of an ice bath duringthe addition. After stirring for 75 min, the product was filtered,washed with water and then dried under vacuum at 70 C.

Example 38 Preparation of 3-amino-1,2,4-triazol-5-yl disulfide sulfatesalt

Concentrated H2SO4 was added to a stirring mixture of 180.0 g3-amino-1,2,4-triazole-5-thiol and 2958 g of water. A 30% hydrogenperoxide solution (87.8 g) was added and stirring was continuedovernight. A peroxide test strip showed that all of the peroxide wasconsumed. The product is a solution of 3-amino-1,2,4-triazol-5-yldisulfide hydrogen sulfate.

Example 39 Preparation of 1,2,4-triazol-3-yl disulfide

Glacial acetic acid (7.89 g) was added to 18.7 g of a 15% aqueoushydrogen peroxide solution. The resulting solution was added slowly to asolution prepared from 16.5 g 1,2,4-triazole-3-thiol, 160 g of water and16.3 g 40% NaOH. The reaction temperature was moderated with the use ofan ice bath during the addition. After stirring overnight at roomtemperature, the product was filtered, washed with water and then driedunder vacuum at 70 C.

Examples 40 to 45 Preparation of Modified Fillers

These examples illustrate the preparation of the modified filler of thepresent invention with an adsorbed group. A carbon black with an iodinenumber of 119 and a DBPA of 125 mL/100 g was used. The compound listedwas dissolved in about 1 L of solvent and mixed with 150 g of the carbonblack for about 15 minutes. The solvent was then removed with a rotaryevaporator and dried under vacuum at 70 C. Portions of some samples weresubjected to Soxhlet extraction overnight with methanol, and analyzedfor sulfur to confirm adsorption. The resulting S analysis showed thatthe adsorbed compounds were nearly completely removed, thus confirmingadsorption and not attachment.

Amount, Example Compound g Solvent 40 3-amino-1,2,4-triazole-5-thiol4.33 Methanol 41 3-amino-1,2,4-triazole-5-thiol 4.31 Methanol 423-amino-1,2,4-triazol-5-yl disulfide 4.32 Methanol 433-amino-1,2,4-triazol-5-yl disulfide 4.33 Methanol 441,2,4-triazole-3-thiol 3.78 Methanol 45 1,2,4-triazol-3-yl disulfide3.76 Methanol

Example 46 Preparation of a Modified Filler

A mixture of 5.00 g 3-amino-1,2,4-triazol-5-yl disulfide, 0.70 g sulfurand 5.34 g N-methylpyrrolidone was heated to 100 C. with stirring. Somesolid material was broken up with a spatula as the sample heated. All ofthe sulfur had reacted after heating at 100 C. for an hour. The samplewas cooled and the resulting solid was washed with 5 g of water anddried. HPLC/MS analysis showed that the product,3-amino-1,2,4-triazol-5-yl trisulfide, also contained3-amino-1,2,4-triazol-5-yl disulfide and 3-amino-1,2,4-triazole-5-thiol.The product (8.67 g and 52% non-volatile material) was dissolved in hotdimethylformamide and mixed with 137 g of a carbon black with an iodinenumber of 119 and a DBPA of 125 mL/100 g. After stirring for about 15min, the mixture was cooled to room temperature and filtered. The solidswere washed three times with 1 L of water and dried under vacuum at 70C. Adsorbed groups were confirmed to be on the filler.

Example 47 Preparation of a Modified Filler

4-Amino-3-hydrazino-1,2,4-triazole-5-thiol (5.48 g) was dissolved in asolution of 1 L water and 3.0 g NaOH. A carbon black (150 g) with aniodine number of 119 and a DBPA of 125 mL/100 g was added, and themixture was stirred. The pH was reduced to 7.2 on addition of 7.2 gconcentrated sulfuric acid. The mixture was filtered, washed with about3.5 L of water and dried under vacuum at 70 C. Absorbed groups wereconfirmed to be on the filler.

Example 48 Preparation of a Modified Filler

This example illustrates the preparation of a modified filler of thepresent invention, having a PAH 22 content of 25 ppm compared to a PAH22 content of 710 ppm for a reference carbon black. The carbon black hadan iodine number of 137 and a DBPA of 120 mL/100 g. A mixture of the 150g of the carbon black, 4.32 g of 3-amino-1,2,4-triazol-5-yl disulfideand 1 L of methanol was stirred for 15 minutes. The methanol was removedon a rotary evaporator, and the product was dried under vacuum at 70° C.Absorbed groups were confirmed to be on the filler.

Example 49 Preparation of a Modified Filler

A 20 L Ross mixer was charged with 11.26 kg of water and 3.00 kg ofcarbon black and 1543 g of a 0.243 mmol/g solution of3-amino-1,2,4-triazol-5-yl disulfide sulfate salt. The carbon black hadan iodine number of 119 and a DBPA of 125 mL/100 g. After heating to 70°C., 259 g of a 20% solution of NaNO₂ in water was added over 10 min. Themixture was allowed to stir at 70° C. for an hour, and was cooled toroom temperature. An aqueous 40% NaOH solution (37.6 g) was added andthe mixture was stirred an additional 5 min. The mixture was filtered,and the product was washed with water until the conductivity was about5000 uS/cm. The product was dried at 100° C. The product had 1.35 wt %S. A sample of the modified carbon black product that had been subjectedto Soxhlet extraction with methanol overnight had 1.04 wt % S, comparedto 0.75 wt % S for the untreated carbon black. The sample thus hadattached and adsorbed triazoles.

Example 50 Preparation of a Modified Filler

This modified carbon black product was prepared by substantially thesame method as in Example 49.

Example 51 Preparation of a Modified Filler

This example illustrates the preparation of a modified filler of thepresent invention. A batch pelletizer having a mixing chamber with a 8″diameter and 8″ length was heated to 50 C. and charged with 224 g of afluffy carbon black with an iodine number of 149 and a DBPA of 125mL/100 g. Water (17 g) and 132 g of a 0.235 mmol/g solution of3-amino-1,2,4-triazol-5-yl disulfide sulfate salt was added and themixture was mixed at 500 rpm for 1 minute. A 4.21 wt % solution of NaNO₂(107 g) was sprayed in and processing was continued for an additional 5min. The product was dried in an oven at 100° C. A sample of themodified carbon black product that had been subjected to Soxhletextraction with methanol overnight had 0.79 wt % S, compared to 0.47 wt% S for the untreated carbon black. The sample had attached and adsorbedtriazoles.

Example 52 Preparation of a Modified Filler

This example illustrates the preparation of a modified filler of thepresent invention. A carbon black with an iodine number of 70 and a DBPAof 118 mL/100 g was used. A solution of 1.56 g NaNO₂ in 13.2 g of waterwas added over a period of about five minutes to a stirring mixture of150 g of the carbon black, 1300 g water and 47.5 g of a 0.241 mmol/gsolution of 3-amino-1,2,4-triazol-5-yl disulfide sulfate salt at 70 C.The mixing was continued for 65 minutes at 70° C. The mixture was cooledto room temperature and adjusted to a pH of 7.4 with 1.28 g of 40%aqueous NaOH solution. The product was collected by filtration, washedwith 2 L of water and dried under vacuum at 70° C. The carbon blackproduct (120.0 g) was suspended in 663 g of methanol, and 3.4 g of3-amino-1,2,4-triazol-5-yl disulfide was added. After stirring for 15min, the methanol was removed on a rotary evaporator, and the productwas dried under vacuum at 70° C. A sample of the modified carbon blackproduct that had been subjected to Soxhlet extraction with methanolovernight had 1.41 wt % S, compared to 1.31 wt % S for the untreatedcarbon black. The sample thus had attached and adsorbed triazoles.

Example 53 Preparation of a Modified Filler

This example illustrates the preparation of a modified carbon blackproduct of the present invention. It had a PAH 22 content of 25 ppmcompared to a PAH 22 content of 710 ppm for a reference carbon black.The carbon black had an iodine number of 137 and a COAN of 120 mL/100 g.A solution of 2.60 g NaNO₂ in 24.7 g of water was added over a period ofsix minutes to a stirring mixture of 150 g of the carbon black, 1300 gwater, 4.31 g 3-amino-1,2,4-triazol-5-yl disulfide and 5.14 g 70%methanesulfonic acid at 70° C. The mixing was continued for 66 minutesat 70° C. The mixture was cooled to room temperature. The product wascollected by filtration, washed with 2.5 L of water and dried undervacuum at 70° C. A sample of the modified carbon black product that hadbeen subjected to Soxhlet extraction with methanol overnight had 0.77 wt% S, compared to 0.48 wt % S for the untreated carbon black. The samplehad attached and adsorbed triazoles.

Example 54 Preparation of a Carbon Black Product

This example illustrates the preparation of a modified carbon blackproduct of the present invention. A suspension of 1302 g water, 150 gcarbon black and 100 g Clorox sodium hypochlorite solution was mixed andheated to 90 C. The carbon black had an iodine number of 119 and a DBPAof 125 mL/100 g. Mixing was continued for 60 minutes, and the suspensionwas cooled to 70 C. The product was collected by filtration, washed with2.5 L of water and dried under vacuum at 70 C.3-Amino-1,2,4-triazol-5-yl disulfide (3.44 g) was dissolved in about 0.8L of solvent and mixed with 120 g of the carbon black for about 15minutes. The solvent was then removed with a rotary evaporator and driedunder vacuum at 70 C. Portions of the sample was subjected to Soxhletextraction overnight with methanol, and analyzed for sulfur. Theresulting S analysis shows that the compound could be nearly completelyremoved, and thus the triazole was adsorbed on the filler.

Example 55 Preparation of a Modified Silicon Treated Carbon BlackProduct

This example illustrates the preparation of a modified silicon treatedcarbon black product of the present invention. A silicon treated carbonblack with an iodine number of 64, a STSA of 120 m2/g, a DBPA of 157mL/100 g, and a silicon content of 10 wt % was used. The silicon treatedcarbon black (150 g) was stirred for 15 min with a solution of 4.31 g3-amino-1,2,4-triazol-5-yl disulfide in about 1 L of methanol. Thesolvent was removed on a rotary evaporator, and the product was driedunder vacuum at 70° C. Adsorbed groups were confirmed on the filler.

Example 56 Preparation of a Modified Silica Product

This example illustrates the preparation of a modified silica product ofthe present invention. Zeosil 1165 silica (a product of Rhodia) wasstirred for 15 min with a solution of 7.93 g 3-amino-1,2,4-triazol-5-yldisulfide in about 1 L of methanol. The solvent was removed on a rotaryevaporator, and the product was dried under vacuum at 70° C. Adsorbedgroups were confirmed to be on the filler.

Examples 57 to 66 Preparation of Modified Fillers

In these examples, a carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A 10 wt % solution of NaNO₂ in water wasadded over a period of about five minutes to a stirring mixture of 300 gof the carbon black, 2600 g water, the indicated compound and 70%methanesulfonic acid at 70° C. The mixing was continued for about anhour at 70° C. The mixture was cooled to room temperature. As indicatedin the table, some products were purified by filtration followed bywater washing (A) or water washing followed by ethanol and then waterwashes (B). Some products were purified by centrifugation with two orthree exchanges with water (C) or water followed by ethanol and thenwater (D). The products were dried under vacuum at 70° C. The productshad attached organic groups.

Weight of Weight Weight of 70% of compound, CH₃SO₃H, NaNO₂, Ex. Compoundg g g purification 57 3-amino-1,2,4- 6.31 10.3 5.17 Filter (A) triazole58 3-amino-1,2,4- 12.6 20.6 10.34 Centrifuge triazole (C) 593-amino-1,2,4- 18.9 139.7 15.5 Centrifuge triazole (C) 60 4-4′- 9.3110.3 5.18 Filter (B) aminophenyldisulfide 61 4-(trifluoromethyl) 12.110.3 5.16 Filter (B) aniline 62 4-aminobenzamide 10.2 10.3 5.17Centrifuge (C) 63 4-pentylaniline 12.2 10.3 5.17 Filter (B) 644-pentylaniline 24.4 20.6 10.4 Filter (B) 65 4-pentylaniline 36.7 30.915.5 Filter (B) 66 4-aminobenzoic acid 10.3 20.6 5.18 Centrifuge (D)

Examples 67 to 76 Preparation of Modified Fillers

In these examples of the present invention, 3-amino-1,2,4-triazol-5-yldisulfide was adsorbed on carbon black products having attached groupsfrom Examples 57 to 66. In each case, the carbon black product wasstirred with a solution of 4.3 g of 3-amino-1,2,4-triazol-5-yl disulfidein 1 L of ethanol for 15 minutes. The ethanol was removed on a rotaryevaporator, and the product was dried under vacuum at 70° C.

Carbon product with attached organic Example groups, from listed Example67 57 68 58 69 59 70 60 71 61 72 62 73 63 74 64 75 65 76 66

Example 77 Preparation of a Modified Filler

This example illustrates the preparation of a modified filler of thepresent invention. A carbon black with an iodine number of 119 and aDBPA of 125 mL/100 g was used. A solution of 3.88 g NaNO₂ in 35.3 g ofwater was added over a period of about ten minutes to a stirring mixtureof 150 g of the carbon black, 1300 g water, 6.86 g 4-aminobenzylamineand 17.05 g of 70% methanesulfonic acid at 70 C. The mixing wascontinued for 60 minutes at 70° C. The mixture was cooled to roomtemperature and adjusted to a pH of 8.4 with 5.44 g of 40% aqueous NaOHsolution. The product was collected by filtration, washed with 2.5 L ofwater and dried under vacuum at 70° C. The carbon black product (120.1g) was suspended in 660 g of methanol, and 3.47 g of3-amino-1,2,4-triazol-5-yl disulfide was added. After stirring for 15min, the methanol was removed on a rotary evaporator, and the productwas dried under vacuum at 70° C. Adsorbed groups were confirmed to be onthe filler.

Example 78 Preparation of Benzoimidazol-2-yl disulfide

A solution prepared from 10.0 g 2-mercaptobenzoimidazole, 88 g ethanoland 6.68 g 40% aqueous NaOH was mixed with a solution of 8.54 g iodinein 79 g of ethanol. The resulting mixture was filtered, and thecollected product was washed with ethanol and dried under vacuum at 70°C.

Example 79 Preparation of 2-amino-1,3,4-thiadiazol-5-yl disulfide

A solution prepared from 10.0 g 2-amino-1,3,4-thiadiazole-5-thiol, 81 gethanol and 7.78 g 40% aqueous NaOH was mixed with a solution of 9.48 giodine in 75 g of ethanol. The resulting mixture was filtered, and thecollected product was washed with ethanol and dried under vacuum at 70°C.

Example 80 Preparation of 1,2,3-triazole-4-thiol

Concentrated HCl (12.06 g) was added to a solution of 14.98 g5-mercapto-1,2,3-triazole sodium salt in 104 g of ethanol. Solids wereremoved by filtration and the resulting solution of1,2,3-triazole-4-thiol was used directly.

Example 81 Preparation of (1,2,4-triazol-3-ylmethyl)disulfide

3-Chloromethyl-1,2,4-triazole was prepared by a method similar to thatdescribed in J. Am. Chem. Soc. 77 1540 (1955). The3-chloromethyl-1,2,4-triazole was reacted with 1 equivalent of thioureain 30 parts by volume of refluxing ethanol for 15 hr by a method similarto that described in WO2008151288. The reaction product was hydrolyzedwith 12% aqueous NaOH for 20 min at 50° C. Addition of 0.5 eq of I2 andNaI gave (1,2,4-triazol-3-ylmethyl)disulfide.

Comparative Example 82

This material is the carbon black with an iodine number of 70 and a DBPAof 118 mL/100 g used in Example 52.

Comparative Example 83

This material is the carbon black with an iodine number of 149 and aDBPA of 125 mL/100 g used in Example 51 that has been pelletized withwater and dried at 100° C.

Comparative Example 84

This material is the silicon treated carbon black with an iodine numberof 64, a STSA of 120 m2/g. a DBPA of 157 mL/100 g and a silicon contentof 10% that was used in Example 55.

Comparative Example 85

This is the Zeosil 1165 silica used in Example 56.

Comparative Example 86

This material is the carbon black used in Example 53. It had a PAH 22content of 25 ppm compared to a PAH 22 content of 710 ppm for areference carbon black. The carbon black had an iodine number of 137 anda COAN of 120 mL/100 g.

Comparative Example 87

A dry mixture of 4.31 g 3-amino-1,2,4-triazol-5-yl disulfide and 150 gof a carbon black with an iodine number of 119 and a DBPA of 125 mL/100g were mixed in a Waring blender for 30 seconds.

Examples 88 to 100 Preparation of Materials

These examples illustrate the preparation of various materials. A carbonblack with an iodine number of 119 and a DBPA of 125 mL/100 g was used.The compound listed was dissolved in about 1 L of solvent and mixed with150 g of the carbon black for about 15 minutes. The solvent was thenremoved with a rotary evaporator and dried under vacuum at 70 C.

Amount, Example Compound g Solvent 88 3-Amino-5-methylthio-1,2,4- 4.90Methanol (comparative) triazole 89 4,4′-Aminophenyl disulfide 4.66Methanol (comparative 90 3-Amino-1,2,4-triazole 3.15 Methanol(comparative) 91 1,2,4-Triazole 2.59 Methanol (comparative) 92 1,2,3Triazole 2.59 Methanol (comparative) 93 1,2,3-triazole-4-thiol 3.74Ethanol (comparative) 94 2-Mercaptobenzothiazole 6.26 CH2Cl2(comparative) 95 2-Mercaptobenzoimidazole 5.62 Methanol (comparative) 961,2,3-triazol-4-yl disulfide 3.20 Methanol (comparative) 972,5-Dimercapto1,3,4 thiadiazole 5.62 Methanol (comparative) 982-Amino-5-mercapto-1,3,4- 4.99 Acetone (comparative) thiadiazole 99(1,2,4-triazol-3-ylmethyl) disulfide 4.28 Methanol (present invention)100 Benzotriazole 4.47 Methanol (comparative)

Example 101 Preparation of a Comparative Material

This example illustrates the preparation of a comparative material. Acarbon black with an iodine number of 119 and a DBPA of 125 mL/100 g wasused. Benzoimidazol-2-yl disulfide (5.62 g) was dissolved in about 1 Lof hot dimethylformamide and mixed with 150 g of the carbon black forabout 15 minutes. The mixture was cooled, and filtered. The product waswashed three times with water and dried under vacuum at 70° C.

Example 102 Preparation of a Comparative Material

This example illustrates the preparation of a comparative material. Acarbon black with an iodine number of 119 and a DBPA of 125 mL/100 g wasused. 2-Amino-1,3,4-thiadiazoly-5-yl disulfide (4.95 g) was dissolved inabout 700 mL of dimethylsulfoxide and mixed with 150 g of the carbonblack for about 15 minutes. Water (500 g) was added and the mixture wasstored in a refrigerator for three days. The mixture was filtered,washed with 4 L of water and dried under vacuum at 70° C.

Example 103 Preparation of a Comparative Material

This example illustrates the preparation of a comparative carbon blackproduct. A carbon black with an iodine number of 119 and a DBPA of 125mL/100 g was used. A solution of 2.59 g NaNO₂ in 21.3 g of water wasadded over a period of five minutes to a stirring mixture of 150 g ofthe carbon black, 1300 g water, 4.33 g 3-amino-1,2,4-triazol-5-yldisulfide and 5.15 g 70% methanesulfonic acid at 70° C. The mixing wascontinued for 65 min at 70° C. The mixture was cooled to roomtemperature. The product was collected by filtration, washed with 3 L ofwater, 2 L of methanol and dried under vacuum at 70° C. The product has1.06 wt % S. A sample of the carbon black product that had beensubjected to Soxhlet extraction with methanol had 0.97 wt % S, comparedto 0.75 wt % S for the untreated carbon black. Thus, the sample hasattached triazoles and residual extractable material remaining on thesurface.

Performance Characteristics of Elastomeric Composites.

The following examples relate to the use of the modified fillers of thepresent invention or comparative fillers in elastomeric formulations toform elastomeric composites. Several different elastomeric formulationswere used, depending upon the filler. Unless stated otherwise, themethod of preparing the elastomeric composites was the same as inExamples 15-36 described earlier.

Formulations (in Phr, Unless Stated Otherwise):

Formulation AA (Formulation AA was used for examples 29, 40, 42, 45, 88,82, 52, 41, 43, 54, 89, 90, 46, 102, 87, 91-96, 47, 97, 98, 44, 49, 57,67, 58, 68, 59, 69, 60, 70, 61, 71, 62, 72, 63, 73, 64, 74, 65, 75, 66,76, 77, 83, 51, 86, 53, 48, 100, 102, 103, and 99, where carbon blackwas used as the filler or the filler that was modified)

Duradene 739 100 Carbon Black (of indicated Example #) 50 Zinc oxide 3Stearic acid 2 Santoflex 6PPD 1 Sulfur 1.75 Santocure CBS 1.25 PerkacitMBT 0.2Formulation BB (Formulation BB was used for examples Table XIV for ATTand ATT2 wherein the chemical group (the triazole) was added duringcompounding as a comparative)These samples had triazoles added during compounding:

Formulation BB #1 #2 Duradene 739 100 100 Carbon Black (of indicatedExample #) 50 50 3-amino-1,2,4-triazole-5-thiol 1.453-amino-1,2,4-triazol-5-yl disulfide 1.44 Zinc oxide 3 3 Stearic acid 22 Santoflex 6PPD 1 1 Sulfur 1.75 1.75 Santocure CBS 1.25 1.25 PerkacitMBT 0.2 0.2Formulation CC (Formulation CC was used for Examples 85, 56, 84, and 55,where the filler was silica or silicon-treated carbon black (the presentinvention or comparatives thereof)

Formulation CC #1 #2 #3 #4 Duradene 739 100 100 100 100 SiO2 (Ex. 85) 56Ex. 56 56 Silicon-treated filler (Ex. 84) 50 Ex. 55 50bis(triethoxysilylpropyl)polysulfide 4.48 4.48 2 2 Zinc oxide 3 3 3 3Stearic acid 2 2 2 2 Santoflex 6PPD 1 1 1 1 Sulfur 1.5 1.5 1.5 1.5Santocure CBS 1.7 1.7 1.4 1.4 Diphenylguanidine 1.5 1.5 0.7 0.7

Table VIII provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude modified fillers of the present invention having an adsorbedcompound of 3-amino-1,2,4-triazole-5-thiol or3-amino-1,2,4-triazol-5-yl-disulfide in comparison with unmodifiedcarbon black (Example 29).

TABLE VIII Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 14% slip at 21% slip 29 100 100 100 4093 183 143 42 94 173 145

Both samples that included the modified carbon black (Examples) showedimproved (lower) relative tan delta values and increased relativeabrasive indices. As discussed above, lower relative tan delta valuesare desirable, as they reflect reduced heat build up in the elastomercomposite when subjected to cyclic strain. A higher relative abrasiveindex also is desirable and reflects improved abrasion resistance.

Table IX provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude a carbon black product of the present invention having anadsorbed compound of 1,2,4-triazol-3-yl-disulfide in comparison with anunmodified carbon black (Example 29) and a comparative carbon blackproduct having an adsorbed compound not of 1,2,4-triazol-3-yl-disulfide.

TABLE IX Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 29 100 100 100 45 105 233206 88 106 69 67 (comparative)

The sample that included a modified carbon black having an adsorbedcompound of 1,2,4-triazol-3-yl-disulfide of the present invention showedsubstantially improved increased relative abrasive indices and tan deltavalue similar to the controls. The comparative carbon black producthaving an adsorbed compound not of 1,2,4-triazol-3-yl-disulfide hadsubstantially depressed abrasion index results.

Table X provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude silica products of the present invention having an adsorbedcompound of 3-amino-1,2,4-triazol-5-yl-disulfide in comparison with anunmodified silica (Example 85).

TABLE X Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 85 (Silica) 100 100 100 56114 150 179

The sample that included a modified silica having the adsorbed compoundof the present invention showed substantially improved increasedrelative abrasion indices and only modest tan delta values increasesrelative to the control.

Table XI provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude a modified silicon treated carbon black product of the presentinvention having an adsorbed compound of3-amino-1,2,4-triazol-5-yl-disulfide in comparison with an unmodifiedsilicon treated carbon black product (Example 84).

TABLE XI Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 84 (silicon-treated 100 100100 carbon black 55 95 140 147

The sample that included a modified silicon treated carbon black producthaving the adsorbed compound of the present invention showedsubstantially improved increased relative abrasion indices relative tothe control.

Table XII provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude a modified carbon black product of the present invention havingan adsorbed compound of 3-amino-1,2,4-triazol-5-yl-disulfide andattached organic groups in comparison with unmodified carbon blacks(Example 82).

TABLE XII Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 82 100 100 100 52 86 178 15529 158 149 133

The sample that included a modified carbon black product of the presentinvention having the adsorbed compound and attached organic groupsshowed substantially improved increased relative abrasion indices andtan delta value improvements relative to the control using the samefiller. Furthermore, the modified carbon black product of the presentinvention having the adsorbed compound and attached organic groups hadimproved increased relative abrasion indices and substantial tan deltaimprovements relative to an untreated carbon black (Example 29) commonlyused for tread compounds.

Table XIII provides performance results (relative tan delta and relativeabrasion indices at 14% slip for elastomeric composites that includecarbon black products of the present invention having an adsorbedcompound in comparison with an unmodified carbon black (Example 29) andcomparative carbon black products having a different adsorbed compound.

TABLE XIII Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 14% slip at 21% slip 29 100 100 100 41100 201 156 43 96 172 143 54 99 165 140 89 111 104 96 (comparative) 9099 89 79 (comparative)

The samples that included a modified carbon black having the adsorbedcompound of the present invention showed substantially improvedincreased relative abrasive indices relative to the control. The samplethat included an oxidized black having the adsorbed compound of thepresent invention showed substantially improved increased relativeabrasive indices relative to the control containing the unmodifiedcarbon black. The comparative carbon black product having a differentadsorbed compound had substantially unchanged or depressed abrasionindex results.

Table XIV provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude an unmodified carbon black (Example 29) and compounds in which3-amino-1,2,4-triazole-5-thiol was added to the mixer withoutpreadsorption on the carbon black.

TABLE XIV Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 29 100 100 100 Add ATT2during 94 79 85 compounding (Form. BB #2) Add ATT during 98 85 94compounding (Form. BB #1)

As shown, the addition of compounds directly to the mixer withoutpreadsorption on carbon black resulted in compounds with poor abrasionindex values.

Table XV provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude a carbon black product of the present invention having theadsorbed compound in comparison with a comparative carbon black producthaving a different adsorbed compound, an unmodified carbon black(Example 29), and a compound in which the compound is previously drymixed with carbon black, but without preadsorption on the carbon black.

TABLE XV Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 29 100 100 100 46 83 159 122102 107 86 64 (comparative) 87 97 81 69 (comparative)

The sample that included the modified carbon black having the adsorbedcompound of the present invention showed substantially improvedincreased relative abrasive indices and an improved tan delta valuerelative to the control. The comparative carbon black product having adifferent adsorbed compound had depressed abrasion index results.Previous dry mixing of the compound with the carbon black withoutadsorption resulted in a compound with poor abrasion index values.

Table XVI provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude an unmodified carbon black (Example 29) and comparative carbonblack products having an adsorbed compound.

TABLE XVI Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 29 100 100 100 91 103 86 92(comparative) 92 106 90 92 (comparative) 93 75 81 109 (comparative)

The comparative carbon black products having an adsorbed compound haddepressed abrasion index results or results similar to that of theuntreated carbon black.

Table XVII provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip) for elastomeric composites thatinclude comparative carbon black products having an adsorbed compound incomparison with an unmodified carbon black (Example 29).

TABLE XVII Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 14% slip at 21% slip 29 100 100 100 9479 91 96 (comparative) 95 100 67 71 (comparative) 96 81 73 90(comparative)

The comparative carbon black products having an adsorbed compound haddepressed abrasion index results.

Table XVIII provides performance results (relative tan delta andrelative abrasion indices at 14% slip for elastomeric composites thatinclude a modified carbon black product of the present invention havingan adsorbed compound in comparison with an unmodified carbon black(Example 29) and comparative carbon black products having a differentadsorbed compound.

TABLE XVIII Relative Relative abrasion Example maximum tan delta indexat 14% slip 29 100 100 47 97 215 97 75 57 (comparative) 98 89 79(comparative)

The sample that included a modified carbon black having the adsorbedcompound of the present invention showed a substantially improvedincreased relative abrasive index and tan delta value similar to thecontrols. The comparative carbon black products having a differentadsorbed compound had depressed abrasion index results

Table XIX provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip) for elastomeric composites thatinclude a carbon black product of the present invention having anadsorbed compound in comparison with unmodified carbon black (Example29).

TABLE XIX Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 29 100 100 100 44 124 157136

The sample that included the modified carbon black of the presentinvention showed improved relative abrasive indices.

Table XX provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude a carbon black product of the present invention having attachedorganic groups and an adsorbed compound in comparison with unmodifiedcarbon black (Example 29).

TABLE XX Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 29 100 100 100 49 69 236 181

The sample that included the modified carbon black of the presentinvention showed improved tan delta performance and improved relativeabrasion indices.

Table XXI provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude modified carbon black products of the present invention havingan adsorbed compound and attached organic groups in comparison with anunmodified carbon black and carbon blacks having attached organic groupsbut no adsorbed compounds.

TABLE XXI Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 14% slip at 21% slip 29 100 100 100 57 95 79 7867 93 139 125 58 83 69 69 68 91 127 112 59 74 59 69 69 89 83 89 60 81 8395 70 71 178 160 61 107 72 72 71 98 184 129

The samples that included a modified carbon black product of the presentinvention having the adsorbed compound and attached organic groups(Examples 67-71) showed improved increased relative abrasion indicesrelative to the carbon blacks having only the same attached organicgroup.

Table XXII provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip for elastomeric composites thatinclude modified carbon black products of the present invention havingan adsorbed compound and attached organic groups in comparison with anunmodified carbon black and carbon blacks having attached organicgroups, but no adsorbed compounds.

TABLE XXII Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 14% slip at 21% slip 29 100 100 100 62116 105 76 72 109 130 89 63 104 115 77 73 91 167 105 64 93 63 60 74 10094 73 65 104 53 49 75 89 78 56 66 101 116 76 76 84 142 101

The samples that included a modified carbon black product of the presentinvention having the adsorbed compound and attached organic groups(Examples 72-76) showed improved increased relative abrasion indicesrelative to the carbon blacks having only the same attached organicgroup.

Table XXIII provides performance results (relative tan delta andrelative abrasion indices at 14% and 21% slip for elastomeric compositesthat include a modified carbon black product of the present inventionhaving an adsorbed compound and attached organic groups in comparisonwith an unmodified carbon black.

TABLE XXIII Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 14% slip at 21% slip 29 100 100 100 7767 209 178

The sample that included a modified carbon black product of the presentinvention having the adsorbed compound and attached organic groupsshowed an improved decreased tan delta value and improved increasedrelative abrasion indices relative to those of the unmodified carbonblack.

Table XXIV provides performance results (relative tan delta and relativeabrasion indices at 14% % slip for elastomeric composites that include amodified carbon black product of the present invention having attachedorganic groups and an adsorbed compound in comparison with unmodifiedcarbon black.

TABLE XXIV Relative Relative abrasion Example maximum tan delta index at14% slip 83 100 100 (comparative) 51 91 184

The sample that included the modified carbon black showed improved tandelta performance and improved relative abrasion indices.

Table XXV provides performance results (relative tan delta and relativeabrasion indices at 14% relative slip) for elastomeric composites thatinclude a modified carbon black product of the present invention havingan adsorbed compound in addition to having attached organic groups. TheTable also shows the performance results of a second carbon blackproduct having an adsorbed compound. The untreated carbon blackreference has a low PAH content.

TABLE XXV Relative maximum Relative abrasion Example tan delta index at14% slip 86 100 100 53 87 171 48 91 107

The sample that included the modified carbon black having the adsorbedcompound (Example 53) and attached organic groups of the presentinvention showed a substantially improved increased relative abrasionindex and an improved tan delta performance relative to the untreatedcarbon black. The sample that included a modified carbon black having anadsorbed compound (Example 48) of the present invention showed animproved increased relative abrasion index relative to the untreatedcarbon black.

Table XXVI provides performance results (relative tan delta and relativeabrasion indices at 14% and 21% slip) for elastomeric composites thatinclude an unmodified carbon black (Example 29) and comparative carbonblack products having an adsorbed compound.

TABLE XXVI Relative Relative abrasion Example maximum tan delta index at14% slip 29 100 100 100 116 99 (comparative) 102 85 78 (comparative)

The comparative carbon black products having an adsorbed compound haddepressed abrasion index results or results similar to that of theuntreated carbon black.

Table XXVII provides performance results (relative tan delta andrelative abrasion indices at 14% and 21% slip for elastomeric compositesthat include an unmodified carbon black (Example 29) and a comparativecarbon black product prepared with adsorbed compound that had beensubsequently substantially removed.

TABLE XXVII Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 14% slip at 21% slip 29 100 100 100 10386 90 99

The sample that included the comparative carbon black products that nolonger had an adsorbed compound did not have improved abrasionperformance.

Table XXIX provides performance results (relative tan delta and relativeabrasion indices at 14% slip) for elastomeric composites that include amodified carbon black product of the present invention having anadsorbed compound in comparison with an unmodified carbon black (Example29)

TABLE XXIX Relative maximum Relative abrasion Example tan delta index at14% slip 29 100 100 99 89 135

The sample that included a modified carbon black having the adsorbedcompound of the present invention showed an improved increased relativeabrasive index and an improved tan delta value relative to the control.

For these remaining examples, Table XXXIII sets forth the formulationsused. The components used in elastomer composites were mixed following atwo-stage mixing in BR Banbury mixer first at a rotor speed of 80 rpmand starting temperature of 50 C followed by the addition of curatives(sulfur, BBTS) in the second stage at a rotor speed of 50 rpm and astarting temperature of 50 C. The components in first-stage were mixedfor a total of 6 minutes before passing through the open mill six times.The milled compound from first-stage mixing was kept at room temperaturefor at least 2 h before second stage mixing. The curatives were thenmixed in the second stage for 2 minutes. Table XXX provides performanceresults (relative tan delta and relative abrasion indices at 7% and 14%slip) for natural rubber composites that include a modified carbon blackproduct of the present invention in comparison with an unmodified carbonblack (Example 29) and an unmodified silica.

TABLE XXX Relative Relative Relative maximum tan abrasion index abrasionindex Example delta at 7% slip at 14% slip 104 100 100 100 105 (Silica)63 66 57 106 73 89 63

The modified carbon black of the present invention had a reduced anddesirable tan delta index relative to the carbon black sample and anincreased and desirable abrasion indicies relative to the silica. At 7%slip, the modified carbon black of the present invention was a favorablecompromise between the untreated carbon black and the untreated silica.

Table XXXI provides performance results (relative tan delta and relativeabrasion indices at 7% and 14% slip) for natural rubber/polybutadienecomposites that include a modified carbon black product of the presentinvention in comparison with an unmodified carbon black (Example 29).

TABLE XXXI Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 7% slip at 14% slip 107 100 100 100 10885 103 70

The modified carbon black of the present invention had a reduced anddesirable tan delta index relative to the carbon black sample and anabrasion index value at 7% slip similar to the control.

Table XXXII provides performance results (relative tan delta andrelative abrasion indices at 7% and 14% slip) for polyisoprenecomposites that include a carbon black product of the present inventionin comparison with an unmodified carbon black (Example 29).

TABLE XXXII Relative Relative Relative maximum tan abrasion indexabrasion index Example delta at 7% slip at 14% slip 109 100 100 100 11075 92 76

The modified carbon black of the present invention had a reduced anddesirable tan delta index relative to the carbon black sample. Theresults for the sample comprising the modified carbon black product ofthe present invention is a favorable compromise between the tan deltaindex and the abrasion index at 7% slip.

TABLE XXXIII Formulations (parts by weight): Example Example ExampleExample Example Example Example Ingredients 104 105 106 109 110 107 108SMR 20 100 100 100 50 50 natural rubber* Natsyn 2000 100 100polyisoprene* Buna CB24 50 50 polybutadiene* Z1165 SiO2 56 (from Ex.85)* V7H control 50 50 50 (Example 29)* Example 50* 50 50 50 Si69(coupling 4.48 4.48 4.48 4.48 4.48 4.48 4.48 agent)* Calight RPO* 2.52.5 2.5 2.5 2.5 2.5 2.5 ZnO* 5 5 5 5 5 5 5 Stearic acid* 3 3 3 3 3 3 3Agerite resin D 1.5 1.5 1.5 1.5 1.5 1.5 1.5 antioxidant* 6PPD 1.5 1.51.5 1.5 1.5 1.5 1.5 (antioxidant)* Akrowax5031* 1.5 1.5 1.5 1.5 1.5 1.51.5 Sulfur** 1.6 1.2 1.2 1.2 1.2 1.2 1.2 BBTS** 2.0 1.4 1.8 1.4 1.8 1.41.8 (accelerator) *Added in Stage 1 compounding **Added in Stage 2compounding

Applicants specifically incorporate the entire contents of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

Other embodiments of the present invention will be apparent to thoseskilled in the art from consideration of the present specification andpractice of the present invention disclosed herein. It is intended thatthe present specification and examples be considered as exemplary onlywith a true scope and spirit of the invention being indicated by thefollowing claims and equivalents thereof.

What is claimed is:
 1. A modified filler comprising a filler havingadsorbed thereon a triazole comprising:

or tautomers thereof; wherein Z_(b) is an alkylene group, where b is 0or 1; X, which is the same or different, is H, NH₂, SH, NHNH₂, CHO,COOR, COOH, CONR₂, CN, CH₃, OH, NDD′, or CF₃; Y is H, or NH₂; A is afunctional group that is S_(k)R, SSO₃H, SO₂NRR, SO₂SR, SNRR′, SNQ,SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), or2-(1,3-dithiolanyl); or a linear, branched, aromatic, or cyclichydrocarbon radical substituted with one or more of said functionalgroup; where R and R′, which are the same or different, are hydrogen;branched or unbranched C₁-C₁₂ alkyl, alkenyl, alkynyl; aryl; heteroaryl;alkylaryl; arylalkyl, arylene, heteroarylene, or alkylarylene; k is aninteger from 1 to 8 when R is H and otherwise k is 2 to 8; Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6; Eis S_(w), where w is 2 to 8, SSO, SSO₂, SOSO₂, SO₂SO₂; and said triazoleis optionally N— substituted with an NDD′ substituent, where D and D′,which are the same or different, are H or C₁-C₄ alkyl.
 2. The modifiedfiller of claim 1, wherein said triazole comprises:

or tautomers thereof, and E is S_(w), where w is 2 to 8, SSO, SSO₂,SOSO₂, SO₂SO₂.
 3. The modified filler of claim 1, wherein said fillerhas adsorbed thereon: 3-amino-1,2,4-triazole-5-thiol,3-amino-1,2,4-triazol-5-yl disulfide, 1,2,4-triazole-3-thiol, or1,2,4-triazol-3-yl disulfide, or any combination thereof.
 4. Themodified filler of claim 1, wherein said triazole comprising:

or tautomers thereof.
 5. A modified filler comprising a filler havingadsorbed absorbed thereon: a) at least one triazole; b) at least onepyrazole; or any combination thereof, wherein said modified fillerimproves abrasion resistance when present in an elastomer compositioncompared to said filler that is not modified.
 6. The modified filler ofclaim 5, wherein a) or b) include a sulfur-containing substituent thatis S_(w), where w is 2 to 8, SSO, SSO₂, SOSO₂, SO₂SO₂.
 7. The modifiedfiller of claim 1, further comprising at least one chemical groupattached to said filler.
 8. The modified filler of claim 7, wherein saidchemical group is at least one organic group, and said organic groupcomprises: a) at least one triazole; b) at least one pyrazole; c) atleast one imidazole; or any combinations thereof.
 9. The modified fillerof claim 8, wherein said triazole is attached to said filler andcomprises:

or tautomers thereof; wherein Z_(b) is an alkylene group, where b is 0or 1; at least one X comprises a bond to the filler, and any remaining Xcomprises a bond to the filler or a functional group that is H, NH₂, SH,NHNH₂, CHO, COOR, COOH, CONR₂, CN, CH₃, OH, NDD′, or CF₃, or is A, R orR′; A is a functional group that is S_(k)R, SSO₃H, SO₂NRR′, SO₂SR,SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),or 2-(1,3-dithiolanyl); or a linear, branched, aromatic, or cyclichydrocarbon radical substituted with one or more of said functionalgroup; where R and R′, which are the same or different, are hydrogen;branched or unbranched C₁-C₁₂ alkyl, alkenyl, alkynyl; aryl; heteroaryl;alkylaryl; arylalkyl, arylene, heteroarylene, or alkylarylene; k is aninteger from 1 to 8 when R is H and otherwise k is 2 to 8; Q is(CH₂)_(w), (CH2)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6; Eis S_(w), where w is 2 to 8, SSO, SSO₂, SOSO₂, SO₂SO₂; and said triazoleis optionally N— substituted with an NDD′ substituent, where D and D′,which are the same or different, are H or C₁-C₄ alkyl.
 10. The modifiedfiller of claim 8, wherein said triazole is attached to said filler andis a 1,2,4-triazol-3-yl group, or a 3-mercapto-1,2,4-triazol-5-yl group.11. The modified filler of claim 7, wherein said chemical groupcomprises an alkyl group or aromatic group having at least functionalgroup that is R, OR, COR, COOR, OCOR, a carboxylate salt, halogen, CN,NR₂, SO₃H, a sulfonate salt, NR(COR), CONR₂, NO₂, PO₃H₂, a phosphonatesalt, a phosphate salt N═NR, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SSO₃H, a SSO₃ ⁻salt, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl) 2-(1,3-dithiolanyl), SOR,or SO₂R, wherein R and R′, which are the same or different, areindependently hydrogen, branched or unbranched C₁-C₁₂, saturated orunsaturated hydrocarbon, and k is an integer that ranges from 1-8, andX⁻ is a halide or an anion derived from a mineral or organic acid, Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where w is an integer from 2 to 6 and x and z areindependently integers from 1 to
 6. 12. The modified filler of claim 7,wherein said chemical group comprises an aromatic group having a formulaAyAr-, wherein Ar is an aromatic radical and A is R, OR, COR, COOR,OCOR, a carboxylate salt, halogen, CN, NR₂, SO₃H, a sulfonate salt,NR(COR), CONR₂, NO₂, PO₃H₂, a phosphonate salt, a phosphate salt N═NR,NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SSO₃H, a SSO₃ ⁻ salt, SO₂NRR′, SO₂SR, SNRR′,SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl)2-(1,3-dithiolanyl), SOR, or SO₂R, wherein R and R′, which are the sameor different, are independently hydrogen, branched or unbranchedC₁-C₁₀₀, saturated or unsaturated hydrocarbon, and k is an integer thatranges from 1-8, and X⁻ is a halide or an anion derived from a mineralor organic acid, Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where w is an integer from2 to 6 and x and z are independently integers from 1 to 6, and y is aninteger from 1 to the total number of —CH radicals in the aromaticradical.
 13. The modified filler of claim 12, wherein said Ar comprisesa triazole group, a pyrazole group, or an imidazole group.
 14. Themodified filler of claim 7, wherein said chemical group is at least oneaminomethylphenyl group.
 15. The modified filler of claim 7, whereinsaid chemical group comprises at least one aromatic sulfide orpolysulfide.
 16. The modified filler of claim 1, wherein said modifiedfiller improves abrasion resistance when present in an elastomercomposition compared to said filler that is not modified with a chemicalgroup adsorbed or attached to said filler.
 17. The modified filler ofclaim 8, wherein said modified filler improves abrasion resistance whenpresent in an elastomer composition compared to said filler that is notmodified and improves (decreases) hysteresis when present in saidelastomer composition compared to said filler that is unmodified.
 18. Amodified filler comprising a filler having attached thereon a triazolecomprising:

or tautomers thereof, wherein wherein Z_(b) is an alkylene group, whereb is 0 or 1; at least one X comprises a bond to the filler and anyremaining X comprises a bond to the filler or a functional group that isH, NH₂, SH, NHNH₂, CHO, COOR, COOH, CONR₂, CN, CH₃, OH, NDD′, or CF₃, oris A, R or R′; A is a functional group that is S_(k)R, SSO₃H, SO₂NRR′,SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), or 2-(1,3-dithiolanyl); or a linear, branched,aromatic, or cyclic hydrocarbon radical substituted with one or more ofsaid functional group; where R and R′, which can be the same ordifferent, are hydrogen; branched or unbranched C₁-C₁₂ alkyl, alkenyl,alkynyl; aryl; heteroaryl; alkylaryl; arylalkyl, arylene, heteroarylene,or alkylarylene; k is an integer from 1 to 8; Q is (CH2)_(w),(CH2)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherex is 1 to 6, z is 1 to 6, and w is 2 to 6; E is S_(w), where w is 2 to8, SSO, SSO₂, SOSO₂, SO₂SO₂; and said triazole is optionally N—substituted with an NDD′ substituent, where D and D′, which are the sameor different, are H or C₁-C₄ alkyl.
 19. An elastomeric compositioncomprising the modified filler of claim 1 and at least one elastomer.20. An article of manufacture comprising the elastomeric composition ofclaim
 19. 21. The article of claim 20, wherein said article is a tire ora component thereof.
 22. A method to improve abrasion resistance in anelastomeric composition comprising introducing at least one modifiedfiller of claim 1 into said elastomeric composition prior to curing. 23.A method to improve (decrease) hysteresis in an elastomeric compositioncomprising introducing at least one modified filler of claim 7 into saidelastomeric composition prior to curing.
 24. A method to increaseabrasion resistance and decrease hysteresis in an elastomericcomposition comprising introducing the modified filler of claim 7 intosaid elastomeric composition prior to curing.